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Stille reaction

The Stille reaction is a chemical reaction widely used in organic synthesis. The reaction involves the coupling of two organic groups, one of which is carried as an organotin compound (also known as organostannanes). A variety of organic electrophiles provide the other coupling partner. The Stille reaction is one of many palladium-catalyzed coupling reactions.
 * Allyl, alkenyl, aryl, benzyl, acyl
 * halides (Cl, Br, I), pseudohalides (OTf, OPO(OR)2), OAc
 * halides (Cl, Br, I), pseudohalides (OTf, OPO(OR)2), OAc

The R1 group attached to the trialkyltin is normally sp2-hybridized, including vinyl, and aryl groups.

These organostannanes are also stable to both air and moisture, and many of these reagents either are commercially available or can be synthesized from literature precedent. However, these tin reagents tend to be highly toxic. X is typically a halide, such as Cl, Br, or I, yet pseudohalides such as triflates and sulfonates and phosphates can also be used. Several reviews have been published.

History
The first example of a palladium catalyzed coupling of aryl halides with organotin reagents was reported by Colin Eaborn in 1976. This reaction yielded from 7% to 53% of diaryl product. This process was expanded to the coupling of acyl chlorides with alkyl-tin reagents in 1977 by Toshihiko Migita, yielding 53% to 87% ketone product. In 1977, Migita published further work on the coupling of allyl-tin reagents with both aryl (C) and acyl (D) halides. The greater ability of allyl groups to migrate to the palladium catalyst allowed the reactions to be performed at lower temperatures. Yields for aryl halides ranged from 4% to 100%, and for acyl halides from 27% to 86%. Reflecting the early contributions of Migita and Kosugi, the Stille reaction is sometimes called the Migita–Kosugi–Stille coupling. John Kenneth Stille subsequently reported the coupling of a variety of alkyl tin reagents in 1978 with numerous aryl and acyl halides under mild reaction conditions with much better yields (76%–99%). Stille continued his work in the 1980s on the synthesis of a multitude of ketones using this broad and mild process and elucidated a mechanism for this transformation. By the mid-1980s, over 65 papers on the topic of coupling reactions involving tin had been published, continuing to explore the substrate scope of this reaction. While initial research in the field focused on the coupling of alkyl groups, most future work involved the much more synthetically useful coupling of vinyl, alkenyl, aryl, and allyl organostannanes to halides. Due to these organotin reagent's stability to air and their ease of synthesis, the Stille reaction became common in organic synthesis.

Mechanism
The mechanism of the Stille reaction has been extensively studied. The catalytic cycle involves an oxidative addition of a halide or pseudohalide (2) to a palladium catalyst (1), transmetalation of 3 with an organotin reagent (4), and reductive elimination of 5 to yield the coupled product (7) and the regenerated palladium catalyst (1). However, the detailed mechanism of the Stille coupling is extremely complex and can occur via numerous reaction pathways. Like other palladium-catalyzed coupling reactions, the active palladium catalyst is believed to be a 14-electron Pd(0) complex, which can be generated in a variety of ways. Use of an 18- or 16- electron Pd(0) source Pd(PPh3)4, Pd(dba)2 can undergo ligand dissociation to form the active species. Second, phosphines can be added to ligandless palladium(0). Finally, as pictured, reduction of a Pd(II) source (8) (Pd(OAc)2, PdCl2(MeCN)2, PdCl2(PPh3)2, BnPdCl(PPh3)2, etc.) by added phosphine ligands or organotin reagents is also common

Oxidative addition
Oxidative addition to the 14-electron Pd(0) complex is proposed. This process gives a 16-electron Pd(II) species. It has been suggested that anionic ligands, such as OAc, accelerate this step by the formation of [Pd(OAc)(PR3)n]−, making the palladium species more nucleophillic. In some cases, especially when an sp3-hybridized organohalide is used, an SN2 type mechanism tends to prevail, yet this is not as commonly seen in the literature. However, despite normally forming a cis-intermediate after a concerted oxidative addition, this product is in rapid equilibrium with its trans-isomer. There are multiple reasons why isomerization is favored here. First, a bulky ligand set is usually used in these processes, such as phosphines, and it is highly unfavorable for them to adopt a cis orientation relative to each other, resulting in isomerization to the more favorable trans product. An alternative explanation for this phenomenon, dubbed antisymbiosis or transphobia, is by invocation of the sdn model. Under this theory, palladium is a hypervalent species. Hence R1 and the trans ligand, being trans to each other, will compete with one palladium orbital for bonding. This 4-electron 3-center bond is weakest when two strong donating groups are present, which heavily compete for the palladium orbital. Relative to any ligand normally used, the C-donor R1 ligand has a much higher trans effect. This trans influence is a measure of how competitive ligands trans to each other will compete for palladium's orbital. The usual ligand set, phosphines, and C-donors (R1) are both soft ligands, meaning that they will form strong bonds to palladium, and heavily compete with each other for bonding. Since halides or pseudohalides are significantly more electronegative, their bonding with palladium will be highly polarized, with most of the electron density on the X group, making them low trans effect ligands. Hence, it will be highly favorable for R1 to be trans to X, since the R1 group will be able to form a stronger bond to the palladium.

Transmetallation
The transmetallation of the trans intermediate from the oxidative addition step is believed to proceed via a variety of mechanisms depending on the substrates and conditions. The most common type of transmetallation for the Stille coupling involves an associative mechanism. This pathway implies that the organostannane, normally a tin atom bonded to an allyl, alkenyl, or aryl group, can coordinate to the palladium via one of these double bonds. This produces a fleeting pentavalent, 18-electron species, which can then undergo ligand detachment to form a square planar complex again. Despite the organostannane being coordinated to the palladium through the R2 group, R2 must be formally transferred to the palladium (the R2-Sn bond must be broken), and the X group must leave with the tin, completing the transmetalation. This is believed to occur through two mechanisms.

First, when the organostannane initially adds to the trans metal complex, the X group can coordinate to the tin, in addition to the palladium, producing a cyclic transition state. Breakdown of this adduct results in the loss of R3Sn-X and a trivalent palladium complex with R1 and R2 present in a cis relationship. Another commonly seen mechanism involves the same initial addition of the organostannane to the trans palladium complex as seen above; however, in this case, the X group does not coordinate to the tin, producing an open transition state. After the α-carbon relative to tin attacks the palladium, the tin complex will leave with a net positive charge. In the scheme below, please note that the double bond coordinating to tin denotes R2, so any alkenyl, allyl, or aryl group. Furthermore, the X group can dissociate at any time during the mechanism and bind to the Sn+ complex at the end. Density functional theory calculations predict that an open mechanism will prevail if the 2 ligands remain attached to the palladium and the X group leaves, while the cyclic mechanism is more probable if a ligand dissociates prior to the transmetalation. Hence, good leaving groups such as triflates in polar solvents favor the cyclic transition state, while bulky phosphine ligands will favor the open transition state. A less common pathway for transmetalation is through a dissociative or solvent assisted mechanism. Here, a ligand from the tetravalent palladium species dissociates, and a coordinating solvent can add onto the palladium. When the solvent detaches, to form a 14-electron trivalent intermediate, the organostannane can add to the palladium, undergoing an open or cyclic type process as above.

Reductive elimination step
In order for R1-R2 to reductively eliminate, these groups must occupy mutually cis coordination sites. Any trans-adducts must therefore isomerize to the cis intermediate or the coupling will be frustrated. A variety of mechanisms exist for reductive elimination and these are usually considered to be concerted.

First, the 16-electron tetravalent intermediate from the transmetalation step can undergo unassisted reductive elimination from a square planar complex. This reaction occurs in two steps: first, the reductive elimination is followed by coordination of the newly formed sigma bond between R1 and R2 to the metal, with ultimate dissociation yielding the coupled product. The previous process, however, is sometimes slow and can be greatly accelerated by dissociation of a ligand to yield a 14-electron T shaped intermediate. This intermediate can then rearrange to form a Y-shaped adduct, which can undergo faster reductive elimination. Finally, an extra ligand can associate to the palladium to form an 18-electron trigonal bipyramidal structure, with R1 and R2 cis to each other in equatorial positions. The geometry of this intermediate makes it similar to the Y-shaped above. The presence of bulky ligands can also increase the rate of elimination. Ligands such as phosphines with large bite angles cause steric repulsion between L and R1 and R2, resulting in the angle between L and the R groups to increase and the angle between R1 and R2 to hence decrease, allowing for quicker reductive elimination.

Kinetics
The rate at which organostannanes transmetalate with palladium catalysts is shown below. Sp2-hybridized carbon groups attached to tin are the most commonly used coupling partners, and sp3-hybridized carbons require harsher conditions and terminal alkynes may be coupled via a C-H bond through the Sonogashira reaction.

As the organic tin compound, a trimethylstannyl or tributylstannyl compound is normally used. Although trimethylstannyl compounds show higher reactivity compared with tributylstannyl compounds and have much simpler 1H-NMR spectra, the toxicity of the former is much larger.

Optimizing which ligands are best at carrying out the reaction with high yield and turnover rate can be difficult. This is because the oxidative addition requires an electron rich metal, hence favoring electron donating ligands. However, an electron deficient metal is more favorable for the transmetalation and reductive elimination steps, making electron withdrawing ligands the best here. Therefore, the optimal ligand set heavily depends on the individual substrates and conditions used. These can change the rate determining step, as well as the mechanism for the transmetalation step.

Normally, ligands of intermediate donicity, such as phosphines, are utilized. Rate enhancements can be seen when moderately electron-poor ligands, such as tri-2-furylphosphine or triphenylarsenine are used. Likewise, ligands of high donor number can slow down or inhibit coupling reactions.

These observations imply that normally, the rate-determining step for the Stille reaction is transmetalation.

Additives
The most common additive to the Stille reaction is stoichiometric or co-catalytic copper(I), specifically copper iodide, which can enhance rates up by >103 fold. It has been theorized that in polar solvents copper transmetalate with the organostannane. The resulting organocuprate reagent could then transmetalate with the palladium catalyst. Furthermore, in ethereal solvents, the copper could also facilitate the removal of a phosphine ligand, activating the Pd center.

Lithium chloride has been found to be a powerful rate accelerant in cases where the X group dissociates from palladium (i.e. the open mechanism). The chloride ion is believed to either displace the X group on the palladium making the catalyst more active for transmetalation or by coordination to the Pd(0) adduct to accelerate the oxidative addition. Also, LiCl salt enhances the polarity of the solvent, making it easier for this normally anionic ligand (–Cl, –Br, –OTf, etc.) to leave. This additive is necessary when a solvent like THF is used; however, utilization of a more polar solvent, such as NMP, can replace the need for this salt additive. However, when the coupling's transmetalation step proceeds via the cyclic mechanism, addition of lithium chloride can actually decrease the rate. As in the cyclic mechanism, a neutral ligand, such as phosphine, must dissociate instead of the anionic X group.

Finally, sources of fluoride ions, such as cesium fluoride, also effect on the catalytic cycle. First, fluoride can increase the rates of reactions of organotriflates, possibly by the same effect as lithium chloride. Furthermore, fluoride ions can act as scavengers for tin byproducts, making them easier to remove via filtration.

Competing side reactions
The most common side reactivity associated with the Stille reaction is homocoupling of the stannane reagents to form an R2-R2 dimer. It is believed to proceed through two possible mechanisms. First, reaction of two equivalents of organostannane with the Pd(II) precatalyst will yield the homocoupled product after reductive elimination. Second, the Pd(0) catalyst can undergo a radical process to yield the dimer. The organostannane reagent used is traditionally tetravalent at tin, normally consisting of the sp2-hybridized group to be transferred and three "non-transferable" alkyl groups. As seen above, alkyl groups are normally the slowest at migrating onto the palladium catalyst. It has also been found that at temperatures as low as 50 °C, aryl groups on both palladium and a coordinated phosphine can exchange. While normally not detected, they can be a potential minor product in many cases. Finally, a rather rare and exotic side reaction is known as cine substitution. Here, after initial oxidative addition of an aryl halide, this Pd-Ar species can insert across a vinyl tin double bond. After β-hydride elimination, migratory insertion, and protodestannylation, a 1,2-disubstituted olefin can be synthesized. Numerous other side reactions can occur, and these include E/Z isomerization, which can potentially be a problem when an alkenylstannane is utilized. The mechanism of this transformation is currently unknown. Normally, organostannanes are quite stable to hydrolysis, yet when very electron-rich aryl stannanes are used, this can become a significant side reaction.

Electrophile
Vinyl halides are common coupling partners in the Stille reaction, and reactions of this type are found in numerous natural product total syntheses. Normally, vinyl iodides and bromides are used. Vinyl chlorides are insufficiently reactive toward oxidative addition to Pd(0). Iodides are normally preferred: they will typically react faster and under milder conditions than will bromides. This difference is demonstrated below by the selective coupling of a vinyl iodide in the presence of a vinyl bromide. Normally, the stereochemistry of the alkene is retained throughout the reaction, except under harsh reaction conditions. A variety of alkenes may be used, and these include both α- and β-halo-α,β unsaturated ketones, esters, and sulfoxides (which normally need a copper (I) additive to proceed), and more (see example below). Vinyl triflates are also sometimes used. Some reactions require the addition of LiCl and others are slowed down, implying that two mechanistic pathways are present. Another class of common electrophiles are aryl and heterocyclic halides. As for the vinyl substrates, bromides and iodides are more common despite their greater expense. A multitude of aryl groups can be chosen, including rings substituted with electron donating substituents, biaryl rings, and more. Halogen-substituted heterocycles have also been used as coupling partners, including pyridines, furans, thiophenes, thiazoles, indoles, imidazoles, purines, uracil, cytosines, pyrimidines, and more (See below for table of heterocycles; halogens can be substituted at a variety of positions on each). Below is an example of the use of Stille coupling to build complexity on heterocycles of nucleosides, such as purines. Aryl triflates and sulfonates are also couple to a wide variety of organostannane reagents. Triflates tend to react comparably to bromides in the Stille reaction.

Acyl chlorides are also used as coupling partners and can be used with a large range of organostannane, even alkyl-tin reagents, to produce ketones (see example below). However, it is sometimes difficult to introduce acyl chloride functional groups into large molecules with sensitive functional groups. An alternative developed to this process is the Stille-carbonylative cross-coupling reaction, which introduces the carbonyl group via carbon monoxide insertion. Allylic, benzylic, and propargylic halides can also be coupled. While commonly employed, allylic halides proceed via an η3 transition state, allowing for coupling with the organostannane at either the α or γ position, occurring predominantly at the least substituted carbon (see example below). Alkenyl epoxides (adjacent epoxides and alkenes) can also undergo this same coupling through an η3 transition state as, opening the epoxide to an alcohol. While allylic and benzylic acetates are commonly used, propargylic acetates are unreactive with organostannanes.

Stannane
Organostannane reagents are common. Several are commercially available. Stannane reagents can be synthesized by the reaction of a Grignard or organolithium reagent with trialkyltin chlorides. For example, vinyltributyltin is prepared by the reaction of vinylmagnesium bromide with tributyltin chloride. Hydrostannylation of alkynes or alkenes provides many derivatives. Organotin reagents are air and moisture stable. Some reactions can even take place in water. They can be purified by chromatography. They are tolerant to most functional groups. Some organotin compounds are heavily toxic, especially trimethylstannyl derivatives.

The use of vinylstannane, or alkenylstannane reagents is widespread. In regards to limitations, both very bulky stannane reagents and stannanes with substitution on the α-carbon tend to react sluggishly or require optimization. For example, in the case below, the α-substituted vinylstannane only reacts with a terminal iodide due to steric hindrance. Arylstannane reagents are also common and both electron donating and electron withdrawing groups actually increase the rate of the transmetalation. This again implies that two mechanisms of transmetalation can occur. The only limitation to these reagents are substituents at the ortho-position as small as methyl groups can decrease the rate of reaction. A wide variety of heterocycles (see Electrophile section) can also be used as coupling partners (see example with a thiazole ring below).

Alkynylstannanes, the most reactive of stannanes, have also been used in Stille couplings. They are not usually needed as terminal alkynes can couple directly to palladium catalysts through their C-H bond via Sonogashira coupling. Allylstannanes have been reported to have worked, yet difficulties arise, like with allylic halides, with the difficulty in control regioselectivity for α and γ addition. Distannane and acyl stannane reagents have also been used in Stille couplings.

Applications
The Stille reaction has been used in the synthesis of a variety of polymers. However, the most widespread use of the Stille reaction is its use in organic syntheses, and specifically, in the synthesis of natural products.

Natural product total synthesis
Larry Overman's 19-step enantioselective total synthesis of quadrigemine C involves a double Stille cross metathesis reaction. The complex organostannane is coupled onto two aryl iodide groups. After a double Heck cyclization, the product is achieved. Panek's 32 step enantioselective total synthesis of ansamycin antibiotic (+)-mycotrienol makes use of a late stage tandem Stille type macrocycle coupling. Here, the organostannane has two terminal tributyl tin groups attacked to an alkene. This organostannane "stitches" the two ends of the linear starting material into a macrocycle, adding the missing two methylene units in the process. After oxidation of the aromatic core with ceric ammonium nitrate (CAN) and deprotection with hydrofluoric acid yields the natural product in 54% yield for the 3 steps. Stephen F. Martin and coworkers' 21 step enantioselective total synthesis of the manzamine antitumor alkaloid Ircinal A makes use of a tandem one-pot Stille/Diels-Alder reaction. An alkene group is added to vinyl bromide, followed by an in situ Diels-Alder cycloaddition between the added alkene and the alkene in the pyrrolidine ring. Numerous other total syntheses utilize the Stille reaction, including those of oxazolomycin, lankacidin C, onamide A, calyculin A, lepicidin A, ripostatin A, and lucilactaene. The image below displays the final natural product, the organohalide (blue), the organostannane (red), and the bond being formed (green and circled). From these examples, it is clear that the Stille reaction can be used both at the early stages of the synthesis (oxazolomycin and calyculin A), at the end of a convergent route (onamide A, lankacidin C, ripostatin A), or in the middle (lepicidin A and lucilactaene). The synthesis of ripostatin A features two concurrent Stille couplings followed by a ring-closing metathesis. The synthesis of lucilactaene features a middle subunit, having a borane on one side and a stannane on the other, allowing for Stille reactionfollowed by a subsequent Suzuki coupling.

Variations
In addition to performing the reaction in a variety of organic solvents, conditions have been devised which allow for a broad range of Stille couplings in aqueous solvent.

In the presence of Cu(I) salts, palladium-on-carbon has been shown to be an effective catalyst.

In the realm of green chemistry a Stille reaction is reported taking place in a low melting and highly polar mixture of a sugar such as mannitol, a urea such as dimethylurea and a salt such as ammonium chloride . The catalyst system is with triphenylarsine:

Stille–carbonylative cross-coupling
A common alteration to the Stille coupling is the incorporation of a carbonyl group between R1 and R2, serving as an efficient method to form ketones. This process is extremely similar to the initial exploration by Migita and Stille (see History) of coupling organostannane to acyl chlorides. However, these moieties are not always readily available and can be difficult to form, especially in the presence of sensitive functional groups. Furthermore, controlling their high reactivity can be challenging. The Stille-carbonylative cross-coupling employs the same conditions as the Stille coupling, except with an atmosphere of carbon monoxide (CO) being used. The CO can coordinate to the palladium catalyst (9) after initial oxidative addition, followed by CO insertion into the Pd-R1 bond (10), resulting in subsequent reductive elimination to the ketone (12). The transmetalation step is normally the rate-determining step. Larry Overman and coworkers make use of the Stille-carbonylative cross-coupling in their 20-step enantioselective total synthesis of strychnine. The added carbonyl is later converted to a terminal alkene via a Wittig reaction, allowing for the key tertiary nitrogen and the pentacyclic core to be formed via an aza-Cope-Mannich reaction. Giorgio Ortar et al. explored how the Stille-carbonylative cross-coupling could be used to synthesize benzophenone phosphores. These were embedded into 4-benzoyl-L-phenylalanine peptides and used for their photoaffinity labelling properties to explore various peptide-protein interactions. Louis Hegedus' 16-step racemic total synthesis of Jatraphone involved a Stille-carbonylative cross-coupling as its final step to form the 11-membered macrocycle. Instead of a halide, a vinyl triflate is used there as the coupling partner.

Stille–Kelly coupling
Using the seminal publication by Eaborn in 1976, which forms arylstannanes from arylhalides and distannanes, T. Ross Kelly applied this process to the intramolecular coupling of arylhalides. This tandem stannylation/aryl halide coupling was used for the syntheses of a variety of dihydrophenanthrenes. Most of the internal rings formed are limited to 5 or 6 members, however some cases of macrocyclization have been reported. Unlike a normal Stille coupling, chlorine does not work as a halogen, possibly due to its lower reactivity in the halogen sequence (its shorter bond length and stronger bond dissociation energy makes it more difficult to break via oxidative addition). Starting in the middle of the scheme below and going clockwise, the palladium catalyst (1) oxidatively adds to the most reactive C-X bond (13) to form 14, followed by transmetalation with distannane (15) to yield 16 and reductive elimination to yield an arylstannane (18). The regenerated palladium catalyst (1) can oxidative add to the second C-X bond of 18 to form 19, followed by intramolecular transmetalation to yield 20, followed by reductive elimination to yield the coupled product (22). Jie Jack Lie et al. made use of the Stille-Kelly coupling in their synthesis of a variety of benzo[4,5]furopyridines ring systems. They invoke a three-step process, involving a Buchwald-Hartwig amination, another palladium-catalyzed coupling reaction, followed by an intramolecular Stille-Kelly coupling. Note that the aryl-iodide bond will oxidatively add to the palladium faster than either of the aryl-bromide bonds.

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Talk:Cheating at Solitaire

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Parkash Singh

Major Parkash Singh VC (31 March 1913 – 23 March 1991) was a Sikh Indian recipient of the Victoria Cross, the highest and most prestigious award for gallantry in the face of the enemy that can be awarded to British and Commonwealth forces.

Biography
Parkash Singh was born on 31 March 1913 in Sharikar village, in the Lyallpur District of what was British India (now modern Pakistan) into a Jat Sikh family. He enlisted in the 8th Punjab Regiment of the British Indian Army on 21 November 1936, seeing service on the North-West Frontier. During the Second World War, Singh was a 28-year-old Havildar serving in the Bren Gun Carrier Platoon of 5th Battalion 8th Punjab Regiment, British Indian Army (now 5th Battalion The Baloch Regiment of Pakistan Army). In January 1943, his battalion was engaged in fighting on the Mayu Peninsula in the Arakan, Burma, against Japanese forces, when the following deed took place for which he was awarded the VC:

 * On 6 January 1943, the Bren Gun Carrier Platoon of 5/8th Punjab was attacked by a strong Japanese patrol near Donbaik on the Mayu Peninsula. The Platoon Commander was wounded and was forced to retire, handing over the command to Havildar Parkash Singh. Parkash Singh noticed two other carriers bogged down in a nullah, and under heavy Japanese fire. He immediately rushed to the rescue of the stricken carriers; calling on their crews to abandon the vehicles and run for safety while he provided covering fire. When his Bren gunner was wounded, he took control of the gun from him, and charged towards the enemy. Driving with one hand and firing the Bren gun with the other, he drove them out of their fixed positions. As he returned to pick the crews of the stranded carriers, he came under heavy enemy fire, but calmly rescued all eight men. On 19 January, the battalion carriers again came under heavy anti-tank fire in the same area, and several of them were destroyed including that of the Platoon Commander. The crews of the destroyed vehicles were given up for dead, and the rest of the carriers withdrew. But Parkash Singh wanted to see for himself if there were any survivors among the burning wrecks. Driving down the beach under intense enemy fire, he found the officer and his driver in their badly damaged carrier. The men were too badly injured to be moved, so Parkash Singh decided to tow their vehicle to safety. Despite the order of his Platoon Commander to go back and save himself, the fearless NCO rigged a makeshift tow chain and secured it to the damaged carrier, all the time exposed to enemy fire, and then towed it back to safety. For his feats of cool courage and selfless devotion on 6 and 19 January 1943, Havildar Parkash Singh was awarded the Victoria Cross although the initial recommendation was for a VC and Bar.

On 15 August 1943, Singh was commissioned in the VCO (Viceroy's Commissioned Officer - the present-day Junior Commissioned Officer) rank of jemadar (now naib subedar), with the war-substantive rank of subedar. Singh remained in the Indian Army post-Independence, transferring to the Sikh Regiment as 8 Punjab had been allotted to the Pakistan Army. Effective 19 July 1948, he was selected for a short-service commission in the rank of lieutenant (seniority from 19 July 1946), and received a regular commission in the same rank on 6 October 1952. He was promoted to captain and then to major on 19 July 1961, retiring on 21 November 1968 after 32 years of service. He died in 1991 aged 77, whilst undergoing heart surgery in England, at Ealing, London. His Victoria Cross is displayed at the Imperial War Museum, London.

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text:
Suzuki reaction

The Suzuki reaction or Suzuki coupling is an organic reaction that uses a palladium complex catalyst to cross-couple a boronic acid to an organohalide. It was first published in 1979 by Akira Suzuki, and he shared the 2010 Nobel Prize in Chemistry with Richard F. Heck and Ei-ichi Negishi for their contribution to the discovery and development of noble metal catalysis in organic synthesis. This reaction is sometimes telescoped with the related Miyaura borylation; the combination is the Suzuki–Miyaura reaction. It is widely used to synthesize polyolefins, styrenes, and substituted biphenyls.

The general scheme for the Suzuki reaction is shown below, where a carbon-carbon single bond is formed by coupling a halide (R1-X) with an organoboron species (R2-BY2) using a palladium catalyst and a base. The organoboron species is usually synthesized by hydroboration or carboboration, allowing for rapid generation of molecular complexity.

Several reviews have been published describing advancements and the development of the Suzuki reaction.

Reaction mechanism
The mechanism of the Suzuki reaction is best viewed from the perspective of the palladium catalyst. The catalytic cycle is initiated by the formation of an active Pd0 catalytic species, A. This participates in the oxidative addition of palladium to the halide reagent 1 to form the organopalladium intermediate B. Reaction (metathesis) with base gives intermediate C, which via transmetalation with the boron-ate complex D (produced by reaction of the boronic acid reagent 2 with base) forms the transient organopalladium species E. Reductive elimination step leads to the formation of the desired product 3 and restores the original palladium catalyst A which completes the catalytic cycle.

The Suzuki coupling takes place in the presence of a base and for a long time the role of the base was not fully understood. The base was first believed to form a trialkyl borate (R3B-OR), in the case of a reaction of a trialkylborane (BR3) and alkoxide (−OR); this species could be considered as being more nucleophilic and then more reactive towards the palladium complex present in the transmetalation step. Duc and coworkers investigated the role of the base in the reaction mechanism for the Suzuki coupling and they found that the base has three roles: Formation of the palladium complex [ArPd(OR)L2], formation of the trialkyl borate and the acceleration of the reductive elimination step by reaction of the alkoxide with the palladium complex.

Oxidative addition
In most cases the oxidative addition is the rate determining step of the catalytic cycle. During this step, the palladium catalyst is oxidized from palladium(0) to palladium(II). The catalytically active palladium species A is coupled with the aryl halide substrate 1 to yield an organopalladium complex B. As seen in the diagram below, the oxidative addition step breaks the carbon-halogen bond where the palladium is now bound to both the halogen (X) as well as the R1 group.

Oxidative addition proceeds with retention of stereochemistry with vinyl halides, while giving inversion of stereochemistry with allylic and benzylic halides. The oxidative addition initially forms the cis–palladium complex, which rapidly isomerizes to the trans-complex.

The Suzuki coupling occurs with retention of configuration on the double bonds for both the organoboron reagent or the halide. However, the configuration of that double bond, cis or trans is determined by the cis-to-trans isomerization of the palladium complex in the oxidative addition step where the trans palladium complex is the predominant form. When the organoboron is attached to a double bond and it is coupled to an alkenyl halide the product is a diene as shown below.

Transmetalation
Transmetalation is an organometallic reaction where ligands are transferred from one species to another. In the case of the Suzuki coupling the ligands are transferred from the organoboron species D to the palladium(II) complex C where the base that was added in the prior step is exchanged with the R2 substituent on the organoboron species to give the new palladium(II) complex E. The exact mechanism of transmetalation for the Suzuki coupling remains to be discovered. The organoboron compounds do not undergo transmetalation in the absence of base and it is therefore widely believed that the role of the base is to activate the organoboron compound as well as facilitate the formation of R1-Pdll-OtBu intermediate (C) from oxidative addition product R1-Pdll-X (B).

Reductive elimination
The final step is the reductive elimination step where the palladium(II) complex (E) eliminates the product (3) and regenerates the palladium(0) catalyst (A). Using deuterium labelling, Ridgway et al. have shown the reductive elimination proceeds with retention of stereochemistry.

The ligand plays an important role in the Suzuki reaction. Typically, the phosphine ligand is used in the Suzuki reaction. Phosphine ligand increases the electron density at the metal center of the complex and therefore helps in the oxidative addition step. In addition, the bulkiness of substitution of the phosphine ligand helps in the reductive elimination step. However, N-heterocyclic carbene ligands have recently been used in this cross coupling, due to the instability of the phosphine ligand under Suzuki reaction conditions. N-Heterocyclic carbenes are more electron rich and bulky than the phosphine ligand. Therefore, both the steric and electronic factors of the N-heterocyclic carbene ligand help to stabilize active Pd(0) catalyst.

Advantages
The advantages of Suzuki coupling over other similar reactions include availability of common boronic acids, mild reaction conditions, and its less toxic nature. Boronic acids are less toxic and safer for the environment than organotin and organozinc compounds. It is easy to remove the inorganic by-products from the reaction mixture. Further, this reaction is preferable because it uses relatively cheap and easily prepared reagents. Being able to use water as a solvent makes this reaction more economical, eco-friendly, and practical to use with a variety of water-soluble reagents. A wide variety of reagents can be used for the Suzuki coupling, e.g., aryl or vinyl boronic acids and aryl or vinyl halides. Work has also extended the scope of the reaction to incorporate alkyl bromides. In addition to many different type of halides being possible for the Suzuki coupling reaction, the reaction also works with pseudohalides such as triflates (OTf), as replacements for halides. The relative reactivity for the coupling partner with the halide or pseudohalide is: R2–I > R2–OTf > R2–Br >> R2–Cl. Boronic esters and organotrifluoroborate salts may be used instead of boronic acids. The catalyst can also be a palladium nanomaterial-based catalyst. With a novel organophosphine ligand (SPhos), a catalyst loading of down to 0.001 mol% has been reported. These advances and the overall flexibility of the process have made the Suzuki coupling widely accepted for chemical synthesis.

Industrial applications
The Suzuki coupling reaction is scalable and cost-effective for use in the synthesis of intermediates for pharmaceuticals or fine chemicals. The Suzuki reaction was once limited by high levels of catalyst and the limited availability of boronic acids. Replacements for halides were also found, increasing the number of coupling partners for the halide or pseudohalide as well. Scaled up reactions have been carried out in the synthesis of a number of important biological compounds such as CI-1034 which used triflate and boronic acid coupling partners which was run on an 80 kilogram scale with a 95% yield.

Another example is the coupling of 3-pyridylborane and 1-bromo-3-(methylsulfonyl)benzene that formed an intermediate that was used in the synthesis of a potential central nervous system agent. The coupling reaction to form the intermediate produced 278 kilograms in a 92.5% yield.

Significant efforts have been put into the development of heterogeneous catalysts for the Suzuki CC reaction, motivated by the performance gains in the industrial process (eliminating the catalyst separation from the substrate), and recently a Pd single atom heterogeneous catalyst has been shown to outperform the industry default homogeneous Pd(PPh3)4 catalyst.

Synthetic applications
The Suzuki coupling has been frequently used in syntheses of complex compounds. The Suzuki coupling has been used on a citronellal derivative for the synthesis of caparratriene, a natural product that is highly active against leukemia:

Metal catalyst
Various catalytic uses of metals other than palladium (especially nickel) have been developed. The first nickel catalyzed cross-coupling reaction was reported by Percec and co-workers in 1995 using aryl mesylates and boronic acids. Even though a higher amount of nickel catalyst was needed for the reaction, around 5 mol %, nickel is not as expensive or as precious a metal as palladium. The nickel catalyzed Suzuki coupling reaction also allowed a number of compounds that did not work or worked worse for the palladium catalyzed system than the nickel-catalyzed system. The use of nickel catalysts has allowed for electrophiles that proved challenging for the original Suzuki coupling using palladium, including substrates such as phenols, aryl ethers, esters, phosphates, and fluorides.

Investigation into the nickel catalyzed cross-coupling continued and increased the scope of the reaction after these first examples were shown and the research interest grew. Miyaura and Inada reported in 2000 that a cheaper nickel catalyst could be utilized for the cross-coupling, using triphenylphosphine (PPh3) instead of the more expensive ligands previously used. However, the nickel-catalyzed cross-coupling still required high catalyst loadings (3-10%), required excess ligand (1-5 equivalents) and remained sensitive to air and moisture. Advancements by Han and co-workers have tried to address that problem by developing a method using low amounts of nickel catalyst (<1 mol%) and no additional equivalents of ligand.

It was also reported by Wu and co-workers in 2011 that a highly active nickel catalyst for the cross-coupling of aryl chlorides could be used that only required 0.01-0.1 mol% of nickel catalyst. They also showed that the catalyst could be recycled up to six times with virtually no loss in catalytic activity. The catalyst was recyclable because it was a phosphine nickel nanoparticle catalyst (G3DenP-Ni) that was made from dendrimers.

Advantages and disadvantages apply to both the palladium and nickel-catalyzed Suzuki coupling reactions. Apart from Pd and Ni catalyst system, cheap and non-toxic metal sources like iron and copper have been used in Suzuki coupling reaction. The Bedford research group and the Nakamura research group  have extensively worked on developing the methodology of iron catalyzed Suzuki coupling reaction. Ruthenium is another metal source that has been used in Suzuki coupling reaction.

Amide coupling
Nickel catalysis can construct C-C bonds from amides. Despite the inherently inert nature of amides as synthons, the following methodology can be used to prepare C-C bonds. The coupling procedure is mild and tolerant of myriad functional groups, including: amines, ketones, heterocycles, groups with acidic protons. This technique can also be used to prepare bioactive molecules and to unite heterocycles in controlled ways through shrewd sequential cross-couplings. A general review of the reaction scheme is given below.

The synthesis of a tubulin-binding compound (antiproliferative agent) was carried out using a trimethoxybenzamide and an indolyl pinacol atoboron coupling partner on a gram scale.

Organoboranes
Aryl boronic acids are comparatively cheaper than other organoboranes and a wide variety of aryl boronic acids are commercially available. Hence, it has been widely used in Suzuki reaction as an organoborane partner. Aryltrifluoroborate salts are another class of organoboranes that are frequently used because they are less prone to protodeboronation compared to aryl boronic acids. They are easy to synthesize and can be easily purified. Aryltrifluoroborate salts can be formed from boronic acids by the treatment with potassium hydrogen fluoride which can then be used in the Suzuki coupling reaction.

Solvent variations
The Suzuki coupling reaction is different from other coupling reactions in that it can be run in biphasic organic-water, water-only, or no solvent. This increased the scope of coupling reactions, as a variety of water-soluble bases, catalyst systems, and reagents could be used without concern over their solubility in organic solvent. Use of water as a solvent system is also attractive because of the economic and safety advantages. Frequently used in solvent systems for Suzuki coupling are toluene, THF, dioxane, and DMF. The most frequently used bases are K2CO3, KOtBu, Cs2CO3, K3PO4, NaOH, and NEt3.

title: Suzuki reaction


text:
Ion-exchange resin

An ion-exchange resin or ion-exchange polymer is a resin or polymer that acts as a medium for ion exchange. It is an insoluble matrix (or support structure) normally in the form of small (0.25–1.43 mm radius) microbeads, usually white or yellowish, fabricated from an organic polymer substrate. The beads are typically porous (with a specific size distribution that will affect its properties), providing a large surface area on and inside them where the trapping of ions occurs along with the accompanying release of other ions, and thus the process is called ion exchange. There are multiple types of ion-exchange resin, that differ in composition if the target is an anion or a cation. Most commercial resins are made of polystyrene sulfonate, followed up by polyacrylate. Ion-exchange resins are widely used in different separation, purification, and decontamination processes. The most common examples are water softening and water purification. In many cases, ion-exchange resins were introduced in such processes as a more flexible alternative to the use of natural or artificial zeolites. Also, ion-exchange resins are highly effective in the biodiesel filtration process.

Types of resins
Most typical ion-exchange resins are based on crosslinked polystyrene. The actual ion-exchanging sites are introduced after polymerisation. Additionally, in the case of polystyrene, crosslinking is introduced by copolymerisation of styrene and a few percent of divinylbenzene. Crosslinking decreases ion-exchange capacity of the resin and prolongs the time needed to accomplish the ion-exchange processes but improves the robustness of the resin. Particle size also influences the resin parameters; smaller particles have larger outer surface, but cause larger head loss in the column processes.

Besides being made as bead-shaped materials, ion-exchange resins are also produced as membranes. These ion-exchange membranes, which are made of highly cross-linked ion-exchange resins that allow passage of ions, but not of water, are used for electrodialysis.

Four main types of ion-exchange resins differ in their functional groups:
 * strongly acidic cation (SAC), typically featuring sulfonic acid groups, e.g. sodium polystyrene sulfonate or polyAMPS, often used for water softening and demineralization operations.
 * strongly basic anion (SBA), typically featuring quaternary amino groups, for example, trimethylammonium groups, e.g. polyAPTAC), good for silica, uranium, nitrates removal.
 * weakly acidic cation (WAC), typically featuring carboxylic acid groups. An ideal choice for dealkalization part and also for softening streams with high salinity levels.
 * weakly basic anion (WBA), typically featuring primary, secondary, and/or tertiary amino groups, e.g. polyethylene amine. Are effective for demineralization where removal of SiO2 and CO2 are not required. Also effective for acid absorption.

Specialised ion-exchange resins are also known such as chelating resins (iminodiacetic acid, thiourea-based resins, and many others).

Anion resins and cation resins are the two most common resins used in the ion-exchange process. While anion resins attract negatively charged ions, cation resins attract positively charged ions.

Anion-exchange resins
Formula: R-OH basic

Anion resins may be either strongly or weakly basic. Strongly basic anion resins maintain their negative charge across a wide pH range, whereas weakly basic anion resins are neutralized at higher pH levels. Weakly basic resins do not maintain their charge at a high pH because they undergo deprotonation. They do, however, offer excellent mechanical and chemical stability. This, combined with a high rate of ion exchange, make weakly base anion resins well suited for the organic salts.

For anion resins, regeneration typically involves treatment of the resin with a strongly basic solution, e.g. aqueous sodium hydroxide. During regeneration, the regenerant chemical is passed through the resin, and trapped negative ions are flushed out, renewing the resin exchange capacity.

Cation-exchange resin
Formula: R−H acidic

The cation exchange method removes the hardness of water but induces acidity in it, which is further removed in the next stage of treatment of water by passing this acidic water through an anion exchange process.

Reaction:
 * R−H + M+ = R−M + H+.

Similar to anion resins, in cation resins the regeneration involves the use of a strongly acidic solution, e.g. aqueous hydrochloric acid. During regeneration, the regenerant chemical passes through the resin and flushes out the trapped positive ions, renewing the resin exchange capacity.

Anion-exchange resin
Formula: –NR4+OH−

Often these are styrene–divinylbenzene copolymer resins that have quaternary ammonium cations as an integral part of the resin matrix.

Reaction:

 * –NR4+OH− + HCl = –NR4+Cl− + H2O.

Anion-exchange chromatography makes use of this principle to extract and purify materials from mixtures or solutions.

Characteristics
Ion exchange resins are often described according to some of the following features.
 * Capacity: Represents the amount of ions that can be exchanged/stored per unit of mass of the resin. Typically is expressed in miligrams of ion per gram of resin (mg/g).
 * Swelling: Into contact with solvent, resins can swell (increase in volume). The swelling behavior of a resin is influenced by its chemical composition, polymer structure, and cross-linking. Resins with a higher degree of cross-linking tend to exhibit lower swelling tendencies compared to those with lower cross-linking. Swelling is typically expressed as the percentage increase in volume or weight of the resin when exposed to a specific solvent.
 * Selectivity: Refers to the resin's preference or ability to selectively adsorb or exchange certain ions over others. It is a fundamental property that determines the resin's effectiveness in separating or removing specific ions from a solution.
 * Stability: The integrity of the resin can be described in terms of mechanical and chemical resilience of the beads.

Pores
The pore media of the resin particles is one of the most important parameters for the efficiency of the product. These pores make different functions depending on Their sizes and are the main feature responsible for the mass transfer between phases making the whole ion exchange process possible. There are three main types of pore sizes:

 * Micropore: With a Slit width less than 2 nm, they are usually found at the end of larger pores and their main characteristic is to have superimposed wall potentials. This means, the particles inside them feel attracted towards their solid walls so they make contact with the active sites.
 * Mesopore: With a Slit width between 2 and 50 nm these mid-size pores have the main objective to withhold capillary condensation and is usually found before the micropores.
 * Macropore: With a Slit width bigger than 50 nm, these are the biggest size pores with the main purpose of being the main path for the molecules to enter the particle and later on redistribute through the other smaller channels

Water softening
In this application, Ion-exchange resins are used to replace the magnesium and calcium ions found in hard water with sodium ions. When the resin is fresh, it contains sodium ions at its active sites. When in contact with a solution containing magnesium and calcium ions (but a low concentration of sodium ions), the magnesium and calcium ions preferentially migrate out of solution to the active sites on the resin, being replaced in solution by sodium ions. This process reaches equilibrium with a much lower concentration of magnesium and calcium ions in solution than was started with.

The resin can be recharged by washing it with a solution containing a high concentration of sodium ions (e.g. it has large amounts of common salt (NaCl) dissolved in it). The calcium and magnesium ions migrate from the resin, being replaced by sodium ions from the solution until a new equilibrium is reached. The salt is used to recharge an ion-exchange resin, which itself is used to soften the water.

Water purification
In this application, ion-exchange resins are used to remove poisonous (e.g. copper) and hazardous metal (e.g. lead or cadmium) ions from solution, replacing them with more innocuous ions, such as sodium and potassium, in the process cation and anion exchange resins are used to remove dissolved ions from the water.

Few ion-exchange resins remove chlorine or organic contaminants from water – this is usually done by using an activated charcoal filter mixed in with the resin. There are some ion-exchange resins that do remove organic ions, such as MIEX (magnetic ion-exchange) resins. Domestic water purification resin is not usually recharged – the resin is discarded when it can no longer be used.

Water of highest purity is required for electronics, scientific experiments, production of superconductors, and nuclear industry, among others. Such water is produced using ion-exchange processes or combinations of membrane and ion-exchange methods.

Ion exchange in metal separation
Ion-exchange processes are used to separate and purify metals, including separating uranium from plutonium and other actinides, including thorium; and lanthanum, neodymium, ytterbium, samarium, lutetium, from each other and the other lanthanides. There are two series of rare-earth metals, the lanthanides and the actinides. Members of each family have very similar chemical and physical properties. Ion exchange was for many years the only practical way to separate the rare earths in large quantities. This application was developed in the 1940s by Frank Spedding. Subsequently, solvent extraction has mostly supplanted use of ion-exchange resins except for the highest-purity products.

A very important case is the PUREX process (plutonium-uranium extraction process), which is used to separate the plutonium and the uranium from the spent fuel products from a nuclear reactor, and to be able to dispose of the waste products. Then, the plutonium and uranium are available for making nuclear-energy materials, such as new reactor fuel and nuclear weapons.

Ion-exchange beads are also an essential component in in-situ leach uranium mining. In-situ recovery involves the extraction of uranium-bearing water (grading as low as 0.05% U3O8) through boreholes. The extracted uranium solution is then filtered through the resin beads. Through an ion-exchange process, the resin beads attract uranium from the solution. Uranium-loaded resins are then transported to a processing plant, where U3O8 is separated from the resin beads, and yellowcake is produced. The resin beads can then be returned to the ion-exchange facility, where they are reused.

The ion-exchange process is also used to separate other sets of very similar chemical elements, such as zirconium and hafnium, which incidentally is also very important for the nuclear industry. Zirconium is practically transparent to free neutrons, used in building reactors, but hafnium is a very strong absorber of neutrons, used in reactor control rods.

Catalysis
Ion exchange resins are used in organic synthesis, e.g. for esterification and hydrolysis. Being high surface area and insoluble, they are suitable for vapor-phase and liquid-phase reactions. Examples can be found where basic (OH−-form) of ion exchange resins are used to neutralize of ammonium salts and convert quaternary ammonium halides to hydroxides. Acidic (H+-form) ion exchange resins have been used as solid acid catalysts for scission of ether protecting groups. and for rearrangement reactions.

Juice purification
Ion-exchange resins are used in the manufacture of fruit juices such as orange and cranberry juice, where they are used to remove bitter-tasting components and so improve the flavor. This allows tart or poorer-tasting fruit sources to be used for juice production.

Sugar manufacturing
Ion-exchange resins are used in the manufacturing of sugar from various sources. They are used to help convert one type of sugar into another type of sugar, and to decolorize and purify sugar syrups.

Pharmaceuticals
Ion-exchange resins are used in the manufacturing of pharmaceuticals, not only for catalyzing certain reactions, but also for isolating and purifying pharmaceutical active ingredients. Three ion-exchange resins, sodium polystyrene sulfonate, colestipol, and cholestyramine, are used as active ingredients. Sodium polystyrene sulfonate is a strongly acidic ion-exchange resin and is used to treat hyperkalemia. Colestipol is a weakly basic ion-exchange resin and is used to treat hypercholesterolemia. Cholestyramine is a strongly basic ion-exchange resin and is also used to treat hypercholesterolemia. Colestipol and cholestyramine are known as bile acid sequestrants.

Ion-exchange resins are also used as excipients in pharmaceutical formulations such as tablets, capsules, gums, and suspensions. In these uses the ion-exchange resin can have several different functions, including taste-masking, extended release, tablet disintegration, increased bioavailability, and improving the chemical stability of the active ingredients.

Selective polymeric chelators have been proposed for maintenance therapy of some pathologies, where chronic ion accumulation occurs, such as Wilson disease (where copper accumulation occurs) or hereditary hemochromatosis (iron overload, where iron accumulation occurs)  These polymers or particles have a negligible or null systemic biological availability and they are designed to form stable complexes with Fe2+ and Fe3+ in the GIT and thus limiting the uptake of these ions and their long-term accumulation. Although this method has only a limited efficacy, unlike small-molecular chelators (deferasirox, deferiprone, or deferoxamine), such an approach may have only minor side effects in sub-chronic studies. Interestingly, the simultaneous chelation of Fe2+ and Fe3+ increases the treatment efficacy.

CO2 Capture from Ambient Air
Anion exchange resins readily absorb CO2 when dry and release it again when exposed to moisture. This makes them one of the most promising materials for direct carbon capture from ambient air, or direct air capture, since the moisture swing replaces the more energy-intensive temperature swing or pressure swing used with other sorbents. A prototype demonstrating this process has been developed by Klaus Lackner at the Center for Negative Carbon Emissions.

title: Ion-exchange resin


text:
VFA-102

Strike Fighter Squadron 102 (VFA-102) is a United States Navy Strike Fighter squadron based at Marine Corps Air Station Iwakuni. Their call sign is Diamond, with the tail code NF, and they fly the F/A-18F Super Hornet.

History
Two distinct squadrons have been designated VF-102. The first VF-102 was established on 1 May 1952 and redesignated VA-36 on 1 July 1955.

The second VF-102 was established in 1955, was eventually redesignated as VFA-102, and is the subject of the remainder of this article.

1950s
Fighter Squadron 102 (VF-102), was established as VA-36 on 1 July 1955, and was immediately redesignated VF-102 on the same day (at the time, squadron designations were associated with their assigned airwing). The squadron was based at NAS Jacksonville flying the F2H Banshee. The squadron's inaugural cruise took place aboard USS Randolph (CV-15) in July 1956. After returning from deployment, the squadron transitioned to the F4D Skyray. In addition to four 20 mm internal cannons, the Skyray carried the new AIM-9 Sidewinder missile.

1960s
The final cruise with the Skyray on Forrestal was January through August 1961 after the squadron had moved to NAS Oceana, Virginia. It subsequently transitioned to the F-4 Phantom beginning a 20-year association with the Phantom.

In 1964 and 1966 VF-102 won the COMNAVAIRLANT Battle "E" efficiency awards. Highlights during this period included participation in Operation Sea Orbit on board USS Enterprise (CVN-65), and combat operations off Vietnam in 1968.

1970s
In 1975 and 1978, VF-102 conducted cross-deck operations aboard HMS Ark Royal. In 1971, 1973, 1974, 1975: the squadron conducted four deployments to the Mediterranean Sea aboard USS Independence as part of Carrier Air Wing Seven, including a port call in Athens, Greece, when they had a political coup; air cover operations during the Yom Kippur War; and recovery of aircraft debris and bodies from TWA Flight 841 that crashed into the Mediterranean Sea after a terrorist bomb exploded in the hold.

1980s
In June 1981 the squadron flew their last Phantom during an Indian Ocean cruise aboard USS Independence (CV-62). During the summer of 1981, the squadron transitioned to the F-14A Tomcat. With the new aircraft, the squadron also received a new mission in addition to their traditional fighter role—photo reconnaissance using the TARPS pod. The squadron deployed aboard USS America (CV-66) in late 1982 to participate in the NATO Exercise Northern Wedding that required high temperature operations in the heavy seas north of the British Isles, garnering considerable attention from Soviet Tu-95D Bear reconnaissance aircraft. The first Tomcat deployment with Carrier Air Wing One began in 1983 and took USS America through the Suez Canal to the Indian Ocean. Two VF-102 Tomcats, flying a routine TARPS mission over Somalia were fired upon by an SA-2 SAM site and AAA in April 1983. Both aircraft returned without damage.

VF-102 deployed in 1984 with the first KA-93 LOROP camera and ARC-182 Have Quick radios, conducting Operational Evaluation for both systems at sea. In 1985, USS America participated in the NATO exercise Ocean Safari and again conducted operations in the challenging seas and low visibility conditions near the Arctic Circle and inside Vestfjord, Norway. While operating northwest of Ireland, a VF-102 TARPS aircrew flew an unprecedented 1200 nm TARPS mission to locate a Soviet Kynda Class Cruiser transiting the English Channel. In March 1986, the squadron deployed on board USS America, headed for the Gulf of Sidra joining USS Saratoga (CV-60) and USS Coral Sea (CV-43) to challenge the Libyan proclaimed Line of Death. A VF-102 Tomcat was first to be fired on by a Libyan SA-5 and AAA while flying Combat Air Patrol for Operation Attain Document. A month later VF-102 flew cover for US Navy and US Air Force bombers in Operation El Dorado Canyon.

1990s
In late 1990, USS America joined USS John F. Kennedy (CV-67) and Saratoga in the Red Sea as part of Operation Desert Shield, arriving the day operations were to begin. USS America remained part of the Red Sea Battle Force until directed to join USS Ranger (CV-61), USS Theodore Roosevelt (CVN-71) and USS Midway (CV-41) in the Persian Gulf. In the six-week campaign, VF-102 logged more than 1400 combat flight hours.

The squadron embarked on USS America again in December 1991 for a six-month deployment to the Mediterranean and Persian Gulf.

In early August 1993, the squadron embarked on USS America to begin their third Mediterranean deployment in three years. During this deployment the squadron conducted humanitarian operations off the coast of Bosnia-Herzegovina supporting Operation Provide Promise and Operation Deny Flight. In late October the squadron supported Operation Restore Hope off the coast of Mogadishu, Somalia. By mid-December they were supporting Operation Southern Watch in Iraq.

In June 1994, the squadron returned to NAS Oceana and transitioned to the F-14B aircraft. The squadron's 1995–1996 Mediterranean cruise began with an emergency sortie to the Adriatic Sea to take part in Operation Deliberate Force. They then proceeded to the Persian Gulf in support of Operation Southern Watch. Placement of U.S. ground forces in Bosnia, led to another America emergency sortie back to the Adriatic in December. The squadron remained in the Adriatic for the remainder of the cruise, logging more than 4,000 hours and over 1,900 traps during the deployment.

With the disestablishment VF-33, VF-102 became America's sole F-14 unit, completing its final deployment on 24 February 1996. Upon America's decommissioning in 1996, VF-102 (and the rest of CVW-1) was assigned to USS George Washington (CVN-73).

In 1997, the squadron deployed aboard George Washington. A port visit to Haifa, Israel was cut short late in November as the carrier battle group was ordered to the Persian Gulf in response to Saddam Hussein's barring UN weapon inspectors from carrying out their assigned tasks. As the crisis grew George Washington joined USS Nimitz (CVN-68) and HMS Invincible (R05). VF-102 returned to Norfolk on 13 March 1998.

In Autumn 1999, VF-102 deployed again to the Persian Gulf in support of Operation Southern Watch over southern Iraq. VF-102 carried out strikes on numerous anti-aircraft and radar sites and conducted numerous TARPS missions.

2000s
On 19 September 2001 in the wake of the September 11 attacks, VF-102 began a scheduled deployment to the Arabian Sea as a part of Operation Enduring Freedom and began combat operations. During that deployment VF-102 flew 5,000 combat hours and dropped 680 bombs as well as guiding more than 50,000 pounds of precision guided munitions launched by other aircraft, VF-102 dropped more ordnance and flew more combat hours than any other F-14 unit during the war in 2001 and 2002. In addition, as part of the USS Theodore Roosevelt Battle Group they were at sea for 159 consecutive days, breaking a 20-year-old record.

Following the return from deployment, the squadron moved to NAS Lemoore, California to begin transition training in the F/A-18F. Upon completion, the squadron again changed homeport to Naval Air Facility Atsugi, Japan.

VFA-102 deployed to the Pacific Ocean aboard USS Kitty Hawk (CV-63) in 2004, 2005, 2006 and 2007, taking part in several military exercises, including Orange Crush, Talisman Saber, Jasex, and Valiant Shield.

In March 2008, VFA-102 was named the Pacific Fleet Battle "E" award winner for the calendar year of 2007, recognizing their readiness to perform wartime tasks amongst all F/A-18E/F squadrons in the Pacific Fleet. In March 2010, the squadron was again awarded the Pacific Fleet Battle "E".

In the spring of 2008, VFA-102 embarked on USS Kitty Hawk for her final deployment. Following a crossdeck in San Diego, the air wing is currently assigned to USS Ronald Reagan (CVN-76).

In 2010, the squadron transitioned to Block II Super Hornets equipped with the AN/APG-79 AESA radar.

In 2021, VFA-102 flew combat missions into Afghanistan as part of the US's Afghanistan retrograde.

title: VFA-102


text: Category:Elections in Macau

title: Category:Elections in Macau


text:
People's Unity Party – Socialist Party

The People's Unity Party – Socialist Party (Sameiningarflokkur alþýðu – Sósíalistaflokkurinn), generally referred to as the Socialist Party (Sósíalistaflokkurinn), was an Icelandic political party that functioned from 1938 to 1968, when the People's Alliance party was created.

History
It was formed through the merger of the Communist Party of Iceland (KFI) and another splinter group from the Social Democratic Party on the grounds that a united front was needed against fascism, according to the guidelines put forth by the Comintern. The formation of the Socialist Party was a result of the Popular Front line embraced by ComIntern, and promoted in Iceland by Einar Olgeirsson of the KFI. Philosopher Jon Olafsson has argued that as it resulted in a split within the larger Social Democratic Party, Comintern did not approve of the merger in its eventual form. This has been contested by historians Thor Whitehead and Hannes H. Gissurarson in books about the communist movement. The Socialist Party maintained cordial relations with the Communist Party of the Soviet Union. In 1939 the chairmanship was taken over by Einar Olgeirsson, after the previous non-communist chairman had left the party in protest against the refusal of his new allies to condemn the attack by the USSR on Finland in the Winter War.

During the Second World War the influence of the party grew. In the 1942 elections it won over its mother organization, the Social Democrats. The Socialist Party clearly supported the formation of the Icelandic Republic in 1944. During the two first years of independence, the Socialist Party took part in a broad coalition government. The coalition broke down on the issue of the claims of the United States to have a military base in Keflavík, which the socialists opposed.

In 1956, the Socialist Party took part in the People's Alliance along with the Egalitarian Society and Hannibal Valdimarsson. When the People's Alliance was made into a formal political party in 1968, the Socialist Party was merged into it and thus became defunct as an independent entity.

title: People's Unity Party – Socialist Party


text:
Talk:M-325

Patent No
Info from Kahn's The Codebreakers: the M-325 patent is one of 2,395,863; 2,552,548; 2,877,565. (I'll check tomorrow.) — Matt 22:52, 29 Nov 2004 (UTC)

Patent 2,877,565
I posted a PDF of most of the patent here: http://www.ilord.com/US2877565A.pdf The patent listed on the main page is not working, at least for me. --Boblord 04:01, 28 May 2006 (UTC)

title: Talk:M-325


text:
Talk:Burning Blue Soul

Fair use rationale for Image:Burning Blue Soul.jpg
Image:Burning Blue Soul.jpg is being used on this article. I notice the image page specifies that the image is being used under fair use but there is no explanation or rationale as to why its use in Wikipedia articles constitutes fair use. In addition to the boilerplate fair use template, you must also write out on the image description page a specific explanation or rationale for why using this image in each article is consistent with fair use.

Please go to the image description page and edit it to include a fair use rationale. Using one of the templates at Fair use rationale guideline is an easy way to insure that your image is in compliance with Wikipedia policy, but remember that you must complete the template. Do not simply insert a blank template on an image page.

If there is other other fair use media, consider checking that you have specified the fair use rationale on the other images used on this page. Note that any fair use images uploaded after 4 May, 2006, and lacking such an explanation will be deleted one week after they have been uploaded, as described on criteria for speedy deletion. If you have any questions please ask them at the Media copyright questions page. Thank you.BetacommandBot 15:58, 1 June 2007 (UTC)

Fair use rationale for Image:Burning Blue Soul.jpg
Image:Burning Blue Soul.jpg is being used on this article. I notice the image page specifies that the image is being used under fair use but there is no explanation or rationale as to why its use in this Wikipedia article constitutes fair use. In addition to the boilerplate fair use template, you must also write out on the image description page a specific explanation or rationale for why using this image in each article is consistent with fair use.

Please go to the image description page and edit it to include a fair use rationale. Using one of the templates at Fair use rationale guideline is an easy way to insure that your image is in compliance with Wikipedia policy, but remember that you must complete the template. Do not simply insert a blank template on an image page.

If there is other fair use media, consider checking that you have specified the fair use rationale on the other images used on this page. Note that any fair use images lacking such an explanation can be deleted one week after being tagged, as described on criteria for speedy deletion. If you have any questions please ask them at the Media copyright questions page. Thank you.

BetacommandBot (talk) 04:31, 12 February 2008 (UTC)

Wrong info
1. There was a reissue in 1983, with a different cover than the original - but it was also credited to Matt Johnson. It did not become a "The The" release until 1991 (with yet a third cover.)

2. There are no "remixes" of this album. All three versions are the same.

I'll let somebody else plot how to fix all that - but there you go. —Preceding unsigned comment added by 74.128.190.96 (talk) 19:32, 20 May 2009 (UTC)

title: Talk:Burning Blue Soul


text:
File:VCCecilReginaldNoble.jpg

Photo of Victoria Cross recipient Cecil Reginald Noble, migrated from the Victoria Cross Reference site with permission. Photo submitted by Martin Hornby - (Gallaher Cigarette Cards).

title: File:VCCecilReginaldNoble.jpg


text:
Talk:Mind Bomb

The term "Mind Bomb" is credited to Bob Hunter, a Canadian journalist and one of the founders of Greenpeace. It seems likely the name of the album and the concept are connected, but I haven't found a good reference for that yet. — Preceding unsigned comment added by Andrew-Galvanize-Davies (talk • contribs) 09:10, 4 August 2011 (UTC)

title: Talk:Mind Bomb


text:
Talk:Pink Moon

Fair use rationale for Image:Pink Moon (remastered).jpg
Image:Pink Moon (remastered).jpg is being used on this article. I notice the image page specifies that the image is being used under fair use but there is no explanation or rationale as to why its use in this Wikipedia article constitutes fair use. In addition to the boilerplate fair use template, you must also write out on the image description page a specific explanation or rationale for why using this image in each article is consistent with fair use.

Please go to the image description page and edit it to include a fair use rationale. Using one of the templates at Fair use rationale guideline is an easy way to insure that your image is in compliance with Wikipedia policy, but remember that you must complete the template. Do not simply insert a blank template on an image page.

If there is other other fair use media, consider checking that you have specified the fair use rationale on the other images used on this page. Note that any fair use images uploaded after 4 May, 2006, and lacking such an explanation will be deleted one week after they have been uploaded, as described on criteria for speedy deletion. If you have any questions please ask them at the Media copyright questions page. Thank you.BetacommandBot 09:09, 6 June 2007 (UTC)
 * To better identify a record and the release history of a record, label and sleeve images are necessary. But I will not "fight" against a bot. --Reinhard P. Braun 05:26, 8 June 2007 (UTC)

"Free Ride" versus "Ride"
fixed a title in tracklist. track 9 is called "Ride", not "Free Ride".

coincidental or not, allmusic.com also makes the same mistake on their page for the album. —Preceding unsigned comment added by 82.181.158.103 (talk) 16:49, 8 February 2008 (UTC)

 * All references on the CD inlay (including handwritten lyrics) have it as "Free Ride". Lfh (talk) 23:06, 18 March 2008 (UTC)
 * I own the original version of this record on vinyl. It's called "Ride". zellin t / c' 05:31, 6 April 2010 (UTC)

 * At Esprit's page for the original pressing, they have some (small) images of the labels and the gatefold sleeve. The Side 2 label shows the title as "Ride", but the section of the sleeve with the lyrics shows the title as "Free Ride" (it's just about possible to tell – beneath the first chunk of text in the third column). Given that Drake's own handwritten lyrics refer to the song as "Free Ride", it's likely that the omission of "Free" on the label was a mistake by the record company. Bryter Music, "The official website of the Estate of Nick Drake", lists the title as "Free Ride" here. –CapitalLetterBeginning (talk) 18:02, 6 April 2010 (UTC)
 * Perhaps there's no "right" answer. I'll just add a brief footnote. Lfh (talk) 11:28, 24 May 2010 (UTC)

Fair use rationale for Image:Pink Moon (remastered).jpg
Image:Pink Moon (remastered).jpg is being used on this article. I notice the image page specifies that the image is being used under fair use but there is no explanation or rationale as to why its use in this Wikipedia article constitutes fair use. In addition to the boilerplate fair use template, you must also write out on the image description page a specific explanation or rationale for why using this image in each article is consistent with fair use.

Please go to the image description page and edit it to include a fair use rationale. Using one of the templates at Fair use rationale guideline is an easy way to ensure that your image is in compliance with Wikipedia policy, but remember that you must complete the template. Do not simply insert a blank template on an image page.

If there is other fair use media, consider checking that you have specified the fair use rationale on the other images used on this page. Note that any fair use images lacking such an explanation can be deleted one week after being tagged, as described on criteria for speedy deletion. If you have any questions please ask them at the Media copyright questions page. Thank you.

BetacommandBot (talk) 14:19, 8 March 2008 (UTC)

Wireless Bollinger
Why are wireless bollinger reviews being added to albums? is this to advertise their website? —Preceding unsigned comment added by 59.167.131.204 (talk) 13:12, 22 April 2008 (UTC)

Review on all albums
This review is on all 3 Nick Drake album wiki pages, probably incorrectly. Alternative Press (March 2001, p.88) - "With a voice paradoxically feather-light and grave, [one] of the most beautiful and melancholy albums ever recorded." —Preceding unsigned comment added by 128.146.32.9 (talk) 00:26, 8 December 2009 (UTC)

Outstanding
This article needs a massive overhaul, but holy mother of god, that sound. Nothing else in the world sounds like this. Plenty try to copy, and none come close. — Preceding unsigned comment added by 208.107.42.216 (talk) 07:04, 7 May 2012 (UTC)

At&t Why
I deleted the at&t bit of information in the Album Information section. Unless there is a reference specifically citing the commercial, I do not think any type of advertisement should have a place in this article. His music is far too beautiful to muddy up with information about mindless commercials. — Preceding unsigned comment added by 208.107.42.216 (talk) 07:07, 7 May 2012 (UTC)

Self-link via Rdr that i rem'd
I summarized
 * /* Track listing */ rem self-lk Pink Moon

re my edit to the accompanying article. If and when the Rdr at Pink Moon (song) is overwrit (as an article on the song), the premature lk (annoying at best, and for some users mystifying) should be restored. --Jerzy•t 07:07, 28 April 2013 (UTC)

Series of proposed small fixes
Propose to make the following edits...if no one objects. Add correct John Wood (music producer) link. Remove link to plastic bag - this seems silly. Remove link to filmed - again, not contributing and silly. Remove broken link to VW "Milky Way" video at the bottom. Correct Link to VW Cabriolet, that actually leads to VW Golf. Add chronology of "Five Leaves Left" to box on the right. Pugsly8000 (talk) 15:11, 31 October 2013 (UTC)

 * Sound fair to me. Go ahead, no need to ask permission :) --Soren84 (talk) 21:22, 31 October 2013 (UTC)

Looks good! Elisunshine01 (talk) 16:50, 2 November 2013 (UTC)

Proposed Addition of Media File
I would like to add this ogg file that comes from https://archive.org/details/opensource_audio. Considering it is open source, it is my understanding that a fair-use rationale is not needed. Please correct me if I'm wrong, I don't want a bot taking it out a week later. I think it is an important 2:41 minute interview with John Wood (the only other person in the studio those two recording nights) specifically about Nick and the recording of Pink Moon. It is an excerpt from a 55 minute BBC Radio2 documentary from 2005 narrated by Brad Pitt. The documentary link is https://archive.org/details/BbcRadio2-LostBoyInSearchOfNickDrake. Could I get feedback from other Wikipedians as to their opinion on this? Can I get a consensus to add this media file and/or advice on whether or not I should add a fair use rationale. For clarity, I want to add the 2:41 minute ogg below, not the whole 55 minute documentary. If I get a consensus, I'll add it! Thank you so much! Pugsly8000 (talk) 13:39, 2 November 2013 (UTC)

I think this is a great clip, and will be a great addition to the article. Elisunshine01 (talk) 18:14, 2 November 2013 (UTC)

Proposed Addition of Cover Art and Packaging Section
I would like to propose this addition to the page. Remove the one sentence in "Background & Recording" about cover art and add this new section. Please provide me with feedback and opinions as to whether this should be added. I find it important, but others may not. If I get a consensus, I will add it. Thank you so much! Pugsly8000 (talk) 14:14, 2 November 2013 (UTC)

Keith Morris was the photographer who took Nick Drake's photo for the cover of Bryter Layter and he was commissioned to photograph Nick for the cover of Pink Moon. However, the photos were not used as Nick's hastily deteriorating appearance, hunched figure and blank expression were not considered good selling points. Annie Sullivan, who oversaw the shoot, recalls the difficulty in making a decision around the cover of the LP, "I remember going to talk to him, and he just sat there, hunched up, and even though he didn't speak, I knew the album was called Pink Moon, and I can't remembered how he conveyed it, whether he wrote it down. ... he wanted a pink moon. He couldn't tell me what he wanted, but I had pink moon to go on." Island picked a piece of surrealist Dali-esque art by Michael Trevithick, who was incidentally a friend of Drake's sister. Those involved do not remember Nick talking about the selection, but it is universally considered that he liked it.

John Wood link
I am wondering if there is a way for the John Wood link to look neater and be easier to read than, "John Wood (Music Producer)"? When I went in and tested removing the "music producer" verbiage it then defaults to a wiki page with a list of John Wood's. How can I have it say "John Wood" and have it link to the correct page? Thanks! --Elisunshine01 (talk) 21:48, 2 November 2013 (UTC) Hey Elisunshine... use the following syntax [ [ actual link | what you want to display ] ] (of course without the spaces) Like the link Drake's sister's. Pugsly8000 (talk) 23:37, 2 November 2013 (UTC) Thanks!!! I knew there was a way to do this!! --Elisunshine01 (talk) 02:32, 4 November 2013 (UTC)

Background and Recording EDIT suggestions
I have been working on an edit and expansion of the Background and Recording sections to be completed and added sometime in the next ten days. I plan to split the sections (Background AND Recording), and add additional information to both (supported, of course). Are there any questions, concerns or input? Would it be helpful to present my proposed edits here first for those interested?

Thanks! --Elisunshine01 (talk) 02:42, 4 November 2013 (UTC)

If anyone is interested in taking a look at my sandbox to see what I am working on, here is the link: Elisunshine01-Sandbox Elisunshine01 (talk) 00:01, 5 November 2013 (UTC)

Fantastic work Elisunshine01, nice addition to this page. Pugsly8000 (talk) 01:05, 6 November 2013 (UTC)

Reception and Legacy Edit suggestions
I have been working on an edit to the Reception and Legacy section. I anyone is interested it is in my sandbox: https://en.wikipedia.org/wiki/User:Pugsly8000/sandbox#Reception_and_Legacy

I appreciate your feedback! Pugsly8000 (talk) 20:53, 10 November 2013 (UTC)

 * VERY nice work :-D The article would benefit a lot from what you wrote. The picture of the paper ad works fine too. Fantastic work! --Soren84 (talk) 22:58, 10 November 2013 (UTC)
 * THANK YOU Soren84. I appreciate your feedback. Pugsly8000 (talk) 02:13, 11 November 2013 (UTC)

Looking really good, nice work! --Elisunshine01 (talk) 03:22, 13 November 2013 (UTC)

New Introduction
Considering ongoing edits which have improved page, I would like to see a better intro. I will begin drafting in my sandbox today (11/13/2013), and I am looking forward to feedback and suggestions. --Elisunshine01 (talk) 18:20, 13 November 2013 (UTC)
 * I will help! Let me know when you have a draft and I'll take a look. Good Work! Pugsly8000 (talk) 21:35, 13 November 2013 (UTC)

Request made for B class and high importance assessment.
I think this article is ready for a B class bump. Additionally, I think it should be listed as high importance. It is included on Rolling Stone's 500 Greatest Albums of All Time list along with Drake's previous albums, Bryter Layter and Five Leaves Left which rated in the "High" importance category, when Pink Moon is arguably Drake's most important work for several reasons (it was his last studio album before he died, the song "Pink Moon" was made famous in the VW commercial, etc.). I made the request for B class and Importance review here: WikiProject Albums/Assessment--Elisunshine01 (talk) 08:22, 3 December 2013 (UTC)

@Elisunshine01: The article meets the B-class criteria according to the project guideline. Furthermore, it is ranked 321 at Rolling Stone's list, enough to be rated as high important album according to me.--Вик Ретлхед (talk) 15:20, 16 January 2014 (UTC)

Sputnikmusic review
The Sputnikmusic album review used in the albums rating review box is a user-generated review and should therefore be discarded per the WikiProject Albums style guide. This was already mentioned in the peer review (diff). I've checked the other reviews from that website and none of them are staff reviews, so these shouldn't be used either. I'm going to remove this one now. Thanks — sparklism hey!
 * That's fair enough - I was never entirely happy that the majority of reviews were from minor websites rather than established music papers/websites. There must be reviews from the time of the CD reissues in 1990 and 2000 that can be used, although I won't be able to check until June at the earliest. Ideally I think it might be a good idea to split the contemporary and legacy reviews into separate paragraphs to highlight how critical opinion of the album has altered over time - I'm somewhat annoyed that someone has decided to remove the ratings for the two 1971 reviews from the infobox without any explanation and these appear to be his/her only edits on Wikipedia. Richard3120 (talk) 14:45, 28 February 2014 (UTC)
 * ...in which case I suggest you reinstate them. I agree with your points about the legacy/contemporary reviews too, and there simply has to be more coverage than we've currently got. There's a GA-status article lurking in here somewhere. — sparklism hey! 15:04, 28 February 2014 (UTC)
 * I was going to... ;-) I left a polite request on the editor's talk page asking why they had made the edits, and generously decided to give them a week to reply before I reverted back. Perhaps I'm being over-generous but I'd rather avoid an edit war if I can. Richard3120 (talk) 15:06, 28 February 2014 (UTC)
 * By the way, I agree with you about GA status – it's mainly thanks to the work of Pugsly8000 and Elisunshine01 that the article has been greatly improved in the last six months or so, and they noted that WikiProject Albums intends to get all the albums on Rolling Stone's 500 Greatest Albums of All Time (of which this is one) up to GA status. The difficulty with this album is that only two people were involved in its recording (the principal one of whom has been dead for nearly 40 years), there were only two critical reviews written at the time, and no interviews with the artist, so most of the information has to come from legacy reviews and the three major biographies of Drake. In short, there's not a wealth of information out there. Richard3120 (talk) 15:22, 28 February 2014 (UTC)
 * Thank you Rihard3120 and Sparklism for all your tuning and edits to this important artist's final album. I have been busy and not able to watch this as closely as I would like. However, I commit now to checking it daily. Perhaps for the best really, I'm not sure I would have responded well to the random removal of some reviews that Richard3120 noticed. : )  Pugsly8000 (talk) 01:01, 2 March 2014 (UTC)
 * Looking again at this, I see Sputnikmusic has a different review for Pink Moon which is tagged as "EMERITUS". Since WikiProject Albums/Sources states that for Sputnikmusic "Use staff and emeritus reviews only, recognizable by tag", do other contributors consider this to be a review that we could use for the article? Thanks. — sparklism hey! 13:43, 3 March 2014 (UTC)

title: Talk:Pink Moon


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Charlotte Martin

Charlotte Ann Martin (born October 31, 1976) is an American singer-songwriter and musician who performs predominantly on the piano. She has published several studio albums, two of which have received mainstream commercial releases: 2004's On Your Shore and 2006's Stromata. In 2009, she issued an instrumental piano album titled Piano Trees, which was followed by Dancing on Needles, on February 1, 2011.

Personal life
Martin grew up in Charleston, Illinois. Her father is a music professor at Eastern Illinois University. Martin won the Miss Illinois Teen USA 1994 title on June 26 and went on to compete in the Miss Teen USA pageant in Biloxi, Mississippi, on August 16. She graduated from Eastern Illinois University in 1998 with a bachelor's degree in vocal performance, majoring in opera. In 1999, she moved to Los Angeles. On September 30, 2005, she married musician/producer Ken Andrews. Their first child, a boy, was born on May 4, 2008; their second, a daughter, on March 9, 2011.

Following the birth of her first child, Martin suffered from intercostal neuralgia that left her incapacitated for the better part of a year, causing lengthy delays to the writing and recording process of her album Dancing on Needles.

On August 11, 2017, Martin filed for divorce from Andrews.

Early material
Prior to the release of her major-label debut, On Your Shore, Martin had composed two full-length albums and two EPs. Her first foray into songwriting came in the form of Mystery, Magic & Seeds (1998), an album Martin wrote as a result of a friend's death, which she now considers juvenilia, but which is available for download from archive.org. Her second album, One Girl Army, remained unreleased, though an EP of the same name containing a few selections from the full-length record was published independently in 2000, and Martin still performs some of its content live. The masters for this album are now owned by Martin's former label, RCA Records.

In 2002, Martin independently released a limited-edition EP containing eight tracks, called Test-Drive Songs, which is now out of print but still available for download on her official website.

In 2003, Martin released another EP, titled In Parentheses, on RCA. It contained four tracks, one of which ("Your Armor") would later be included (with an added string arrangement) on On Your Shore.

On Your Shore
On August 10, 2004, On Your Shore, Martin's first full-length album on a major label, RCA, was released. A video for the single "Every Time It Rains" was also issued.

To help promote the album, Martin toured on the Chicks with Attitude tour with Liz Phair, the Cardigans, and Katy Rose in 2004.

Darkest Hour and Veins
While touring, two EPs were released in preparation for Martin's second album, Stromata. The first, Darkest Hour, included a cover of Depeche Mode's "Judas". The second EP, Veins, came out in November 2005.

On May 1, 2006, a DVD of Martin's live recordings, titled Something Like a DVD, was published via Musictoday.

Martin co-wrote and contributed vocals to "Glass Breaker", a song by the Crystal Method, included on the soundtrack to the 2005 romantic drama film London.

Stromata, Orphans, and Piano Trees
On September 12, 2006, Martin issued Stromata on her husband's label, Dinosaur Fight Records.

Martin co-wrote and contributed vocals to the song "Sweet Things" on Tiësto's 2007 album, Elements of Life. She also co-wrote and contributed vocals and piano to the song "Is This How Love's Supposed to Feel" on Ben Lee's 2007 album, Ripe. She co-wrote and contributed vocals to the song "Feed the Monster" by BT. The original song was never released, but a remix by Blue Stahli was.

On November 11, 2008, Martin released the EP Orphans and followed it a year later with the instrumental album Piano Trees.

Dancing on Needles
On February 1, 2011, Martin issued her fourth full-length album, Dancing on Needles. Produced by her husband, Ken Andrews (who had previously worked with Pete Yorn and Beck), the record traces Martin's struggle with intercostal neuralgia, a nerve disorder that had left her incapacitated for much of the previous year. "It was the most difficult period of my life", Martin stated. "The pain was excruciating. I saw countless doctors, was misdiagnosed countless times and prescribed countless medications. Nothing seemed to help. Forget about not being able to work; getting out of bed was a major undertaking. Worst of all, I couldn't nurse, or even lift, my baby. As a new mother, that was devastating".

The album was released on Martin's Test-Drive Records and was preceded by the single "Volcano".

Water Breaks Stone, Rapture
On February 25, 2014, Martin published Water Breaks Stone.

On March 27, 2017, she announced that she would no longer be touring: "At this point in my life, it's not possible for me to mount any long tours or even short ones. I've chosen to be a mommy and that's my first priority. I still plan to be involved in music though and will do one-offs here and there if the timing's right... [T]his is right for me and my family." She held a farewell tour between March and May and released Rapture on May 12, 2017.

Clear Blue Sky, Monotonous Night, and Dawn
On October 5, 2018, Martin released the second of her instrumental piano albums, titled Clear Blue Sky. The following year, two more albums in a similar vein were issued: Monotonous Night on March 8 and Dawn on December 27. Her latest release is the 2023 EP Knives & Bouquets.

Discography
Studio albums
 * Mystery, Magic & Seeds (1998)
 * Solo (2000)
 * On Your Shore (2004)
 * Stromata (2006)
 * Reproductions (2007)
 * Piano Trees (2009)
 * Dancing on Needles (2011)
 * Hiding Places (2012)
 * Water Breaks Stone (2014)
 * Rapture (2017)
 * Clear Blue Sky (2018)
 * Monotonous Night (2019)
 * Dawn (2019)

EPs
 * One Girl Army (2002)
 * Test-Drive Songs (2002)
 * In Parentheses (2003)
 * Darkest Hour (2005)
 * Veins (2005)
 * Stromata (EP version) (2006)
 * Rarities #1-#6 (2006–2009)
 * Orphans (2008)
 * Knives & Bouquets (2023)

Singles

DVDs
 * Something Like a DVD (2005, re-released in 2007 as dual DVD/CD set with B-sides from On Your Shore and Stromata.)
 * "Hiding Places" (2012 dual DVD/CD: live show and documentary plus 8 B-sides)

Additional credits

 * Martin's song "Beautiful Life" from On Your Shore appears in the Maxis computer game The Sims 2: University (The Sims 2 expansion pack), translated into the game's fictional language of Simlish. "Keep Me in Your Pocket", from Stromata, appears in the same fashion in The Sims 2: Bon Voyage.
 * Martin co-wrote and recorded "Glass Breaker" with the Crystal Method. The song appears on the London Movie Soundtrack.
 * Martin has released six "rarity" EPs, called the Rarities series, available for purchase only at live shows. These contain previously unreleased or hard-to-find material.
 * Martin's voice is featured on the Mae album The Everglow, on the tracks "Prologue" and "Epilogue".
 * Martin is the vocalist/pianist and a co-writer in the song "Greater Lights" on the soundtrack of the video game Advent Rising.
 * Martin recorded "Bring On the Day" for the film Sweet Home Alabama.
 * Martin is credited with additional vocals on the song "Inhuman" by Thousand Foot Krutch, from their 2007 album, The Flame in All of Us.
 * Martin's songs "Veins" (from the Veins EP), "The Dance" (from Stromata), and "Wild Horses" (from On Your Shore) were used during the third, fourth, and ninth seasons, respectively, of the television show So You Think You Can Dance.
 * Martin co-wrote and played piano on the song "Is This How Love's Supposed to Feel" on the 2007 Ben Lee album Ripe.
 * Martin co-wrote and sang "Sweet Things" on the 2007 Tiësto album Elements of Life.

title: Charlotte Martin


text: User talk:70.56.160.239

title: User talk:70.56.160.239


text:
User:Jwrosenzweig/Web of trust

Web of trust

I like mav's idea about a web of trust, and I hope someday we have a system here. Until then, I should make some notes to myself. So I will. If you see yourself on my distrust list, before you give me grief about it, consider that this is intended for my own personal use, and that you shouldn't care all that much what some anonymous person thinks of you. For now, no distrusts. I'm upset with some users but it's not productive to focus on them when there are so many I do trust. :-) If you see yourself on my trust list....thanks for being trustworthy. :-)  And if you don't appear here but think you should (in either case), well, I probably just am having an odd day and forgot about my interactions with you. I'll get around to it. :-)

Jwrosenzweig trusts:
 * Alex756
 * Angela
 * Bcorr
 * Camembert
 * Cimon Avaro
 * Cyan
 * DanKeshet
 * Dante Alighieri
 * David Gerard
 * Deb
 * Decumanus
 * DJ Clayworth
 * Dwindrim (Denni)
 * Ed Poor
 * Essjay
 * Fabiform
 * Finlay McWalter
 * Isomorphic
 * Jengod
 * Jdforrester (James F.)
 * Jmabel
 * Kim Bruning
 * Mark Richards
 * Maveric149 (mav)
 * Meelar
 * Menchi
 * Michael Snow
 * Mkmcconn
 * moink
 * Morwen
 * Muriel Gottrop
 * Pfortuny
 * Raul654
 * Redwolf24 (Red)
 * Rmhermen
 * Sannse
 * Silsor
 * Slrubenstein
 * Theresa knott
 * Tim Starling
 * UninvitedCompany
 * Wesley

title: User:Jwrosenzweig/Web of trust