Nickel(O)-mediated hydrocyanation and carbonylation reactions of alkynes with trimethylsilyl(iso)cyanide

✍ Scribed by John J. Eisch; Allen A. Aradi; Kyoung I. Han

• Publisher: Elsevier Science
• Year: 1983
• Tongue: French
• Weight: 195 KB
• Volume: 24
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)81847-x

✦ Synopsis

Under nickel(O) mediation, trimethylsilyl(iso)cyanide serves as both a useful synhydrocyanating agent and a carbonylating agent for alkynes. Metallacyclopentadienes have often been proposed as essential intermediates in the cyclotrimerization of alkynes into benzene derivatives.' Specifically in the case of nickel(O) catalysts, substantial evidence has been adduced for the stepwise formation of nickelacyclopropene,3 nickelacyclopentadiene 4-8 and, in a special case, even nickelacycloheptatriene 738 intermediates in the oligomerization of alkynes (Scheme I). We now wish to report that the stepwise interaction of an alkyne with nickel(O) complexes can both be observed and controlled by employing strong chelating ligands, such as 2,2'-bipyridyl and bis(l,Z-diphenylphosphino)