New metallation and synthetic applications of isonitriles

Abstract

Insertions of isonitriles into silicon-tin linkage of organo-silylstannanes and silicon-silicon linkage of polysilanes are catalyzed by palladium complexes. [(N-2,6-xylylimino)trialkylsilylmethyl]stannanes thus prepared undergo transmetallation with n-butyllithium to generate in situ [(N-2,6-xylylimino)trialkylsilylmethyl]lithiums, which may serve as acyl anion equivalent in organic synthesis. Organozincs undergo the insertion reaction with aryl isocyanides to generate the correspondding α-(N-aryl-imino)alkylzincs, which may be synthetically used. Successive insertions of 1,2-diisocyanoarenes into Grignard reagent result in the formation of quinoxaline oligomers up to hexamer. © 1990, IUPAC.