Copper higher-order

A further improvement in the cuprate-based methodology for producing PGs utilizes a one-pot procedure (203). The CO-chain precursor (67) was first functionalized with zirconocene chloride hydride ia THF. The vinyl zirconium iatermediate was transmetalated direcdy by treatment with two equivalents of / -butyUithium or methyUithium at —30 to —70° C. Sequential addition of copper cyanide and methyUithium eUcited the /V situ generation of the higher order cyanocuprate which was then reacted with the protected enone to give the PG. 

Another way is to dissolve an alkylcopper compound in an alkyllithium solution. Higher order cuprates can also be prepared, as well as non-ate copper reagents. Metallocenes (see p. 53) are usually made by this method ... 

Electrochemical preparation studies on low-dimensional structures of ternary or higher order compounds have appeared in the last few years. For example, whiskers of the quasi-ID copper(I) sulfide series KCuv-jcSa (0 < x < 0.34) were grown by employing electrochemical methods via anodic dissolution of copper electrodes, at 110 C in ethylenediamine solution of polysulfide K2Sn (n = 5, 6) electrolytes and, in some cases, CuCl [165]. 

An important type of mixed cuprate is prepared from a 2 1 ratio of an alkyllithium and CuCN.11 Called higher-order cyanocuprates, their composition is R2CuCNLi2 in THF solution, but it is thought that most of the molecules are probably present as dimers. The cyanide does not seem to be bound directly to the copper, but rather to the lithium cations.12 The dimers most likely adopt an eight-membered ring motif.13... 

Fig. 18 Free energy profiles for the solvent extraction of copper, where L is Acorga P50. The profile shows the free energy of a site on the liquid/liquid interface. All higher-order rate constants are reduced to first-order rate constants by using the concentrations of reactants in either phase. The free energy lost in each cycle can be seen from the difference between 0 and the 10%, 50% and 80% extraction lines on the right of the diagram. The double-headed arrows indicate the rate-limiting free energy difference.

Thienyl(cyano)copper lithium S Cu(CN)Li xhe reagent is obtained by reaction of thiophene with BuLi in THF at - 78° and then with CuCN at - 40°. The reagent is fairly stable and can be stored in THF at - 20° for about 2 months. It is inert, but is readily converted by addition of RLi or RMgX into a higher-order mixed cuprate, which is as efficient as the freshly prepared cuprate."1... 

A large variety of cuprates are known nowadays. They include heteroleptic derivatives R(Y)CuM (Y = alkynyl, halide, amido, alkoxide, thiolato, phosphide M = Li or Mg), and have found widespread application in organic chemistry. Their syntheses and applications are discussed in the other chapters of this book. In addition, compounds in which the copper to lithium (or magnesium) ratio differs from 1 1 are also known examples are R3CuLi2 and the so-called higher order cyanocuprates introduced by Lipshutz et al. [99]. 

So far, only cuprates with a 1 1 copper/lithium ratio have been considered. Treatment of phenyllithium with various substoichiometric quantities of copper bromide in DMS as solvent afforded so-called higher order cuprates, of which two were characterizable by X-ray crystallography. These have the overall stoichiometries Cu2Li3Ph5(DMS)4 and Cu4Li5Ph9(DMS)4 [114, 115). The structure of the former compound in the solid state is shown in Fig. 1.26. 

NMR investigations [129, 132, 133], EXAFS and XANES studies [134-136], and theoretical calculations [127, 137, 138] performed on higher-order cyanocuprates strongly suggested that the cyanide anion was not bound to copper in these R2Cu(CN)Li2 species. Additional evidence was provided by the first X-ray crystal structure determinations of higher-order cyanocuprates ](C(5H4CH2NMe2-2)2 Cu(CN)Li2] [139] (Fig. 1.34) and [(tBu)2Cu(CN)Li2] [130] (Fig. 1.35). 

Quallich and Woodall described the first asymmetric synthesis utilizing a catalytic enantioselective reduction of the ketoester 35 with (S)-terahydro-l-methyl-3,3-diphenyl-lH,3W-pyrrolo[l,2-c][l,3.2]oxazaborole (CBS) to give the desired hydroxyester 36 (90% ee). After mesylation, Sn2 displacement with a higher-order cuprate derived from copper cyanide gave the diaryl r-butyl ester 37 with good chirality transfer. Intramolecular Friedel-Crafts cyclization gave the tetralone 31 in 90% ee (Scheme 7). ... 

Higher order polynuclear complexes are accessible via polytopic macrocyclic monocycles. The tritopic hexaazamacrocycle [27]N603 was recently shown to bind three copper(II) ions, with two triply bridging p-OH groups (28).95... 

Triorganocuprates are ether-soluble reagents which are often referred to as higher order cuprates . Generally prepared from copper(I) cyanide, these reagents undergo the same reactions as diorganocuprates but offer a different reactivity profile (equation 3).3,4... 

---