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

Abstract

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.