Organolithium reagents by reductive decyanation of nitriles with lithium and a catalytic amount of 4,4'-di-tert-butyl-biphenyl in a Barbier-type reaction

Article abstract of DOI:10.1016/S0040-4020(01)87024-1

The reaction of different nitriles 1 with an excess of lithium powder (1:14 molar ratio) and a catalytic amount of 4,4'-di-tert-butylbiphenyl (5 mol %) in the presence of a carbonyl compound (Barbier-type conditions) in THF at low temperature (-30 or -78°C) leads to the corresponding compounds 2 resulting from the coupling between the electrophile and the organolithium intermediate arising from a reductive decyanation of the starting nitrile 1. This new reaction can be also applied to the use of trimethylchlorosilane as electrophile at 0°C.