Copper alkynides

Generally, organocopper compounds can be prepared by transmetallation between copper salts and organometallic reagents such as RLi, RMgX, and RZnX.53,53a,53b Copper alkynides can be obtained by reaction of terminal alkynes... 

The commercial availability of copper(I) cyanide has also provided an attractive alternative to the in situ preparation of copper alkynides, as cyanide functions very well as a non transferable ligand (equation 21 ).48 Unfortunately, the cyanocuprates (14) suffer from a diminished reactivity, similar to alkynylcu-prates, and have not been widely used.3 Other useful residual ligands are SPh,49 Bu S,49 and BuKD.49... 

Lithium alkynylcuprates react with haloallenes to give similar skipped diacetylenes (see below). The related skipped enynes can be prepared by treatment of (pentadienyl)iron(tricarbonyl) halide complexes with dilithium trialkynylcuprates, the compounds being isolated as the iron(tricarbonyl)(diene) complexes (Scheme 4). Further examples of alkylation reactions of copper alkynides are illustrated in Scheme 5. Reaction between a lithium cyanoaikynecuprate and an iodoallene leads to a skipped diacetylene. This useful reaction has been used by Corey in his synthesis of hybridalactone (Scheme 6). °... 

Hydroxybenzothiazole has also been used as a leaving group in allylic displacennent reactions with copper alkynides. Furthermore, the copper alkynides can be us in wet solvents, THF normally being used (Scheme 27). 

Addition of silver or copper alkynides to MnBr(C0)jj(L)5 j results in replacement of the halide by CsCR. The same alkynides... 

The alkylation of j p-carbon can, in principle, involve the alkyne (acetylene) either as the nucleophile or the electrophile. In practice by far the most important process involves the alkyne as nucleophile since the acidity of the alkyne proton (pK = 25) allows the ready formation of alkynide ions. These are excellent nucleophiles and they readily undergo acylation and alkylation with appropriate electrophiles. The recent introduction of palladium-catalyzed reactions, usually involving copper(I) salts but also other cations, has greatly increased the use made of arylation and vinylation reactions. In this chapter only the alkylation of the alkynide ion will be discussed acylation, vinylation and arylation reactions are discussed elsewhere. The alkylation of alkynide anions is a reaction of considerable synthetic use and has been extensively reviewed. ... 

The low acidity of 1-alkynes means that strong bases must be used to form the alkynide ions and that water is not a suitable solvent aqueous solutions have a very low concentration of alkynide ions. Some transition metal alkynides can be prepared by precipitation from aqueous solution because their solubilities are very low. Suitable solvents for the preparation of alkynide ions must be less acidic than the alkyne, and preferably allow the alkyne and the alkynide ion to remain in solution. Liquid ammonia, te-trahydrofuran, ether and hydrocarbons have all been used, particularly the first, the alkynide anion being readily formed by metal amides. Alkynides of many types have been prepared from various metals. Besides Groups I and III, copper(I), silver, gold(I), zinc, mercury and, more recently, aluminum alkynides have been synthesized. The alkynides of Groups I and II have been principally used as nucleophiles in alkylation reactions, but there are now many examples of other metal alkynides in this role. Palladium-catalyzed reactions, as remarked above, have become increasingly important for the reactions of alkynides of metals other than Groups I and II, but these have not usually involved alkylation. 

Lithium alkynides in tetrahydrofuran or dioxane often give substitution products with secondary haloalkanes, while alkynide Grignard reagents do not usually react with haloalkanes except in the presence of other metals such as cobalt and copper. Substitution of iodine or bromine for chlorine in the halo-alkane often leads to an increased yield of the alkylation product and alkanesulfonates may give greater yields than haloalkanes. Scheme 1 illustrates examples of alkylation of haloalkanes and alkyl sulfates with alkynides of Group I metals. 

The reaction of aryl halides with copper(I) alkynides is known as the Castro reaction (equation 3). The reaction has proved to be particularly important in the synthesis of a wide range of tolan and hetero-aromatic alkynes. Vinyl and allenic halides"" can also be used and several reviews of the reaction have been published. " ... 

Alkynylsilanes. Silylation of alkynes and copper(I) alkynides- is promoted by Zn in MeCN (sealed-tube reactions). 

---