Stereoselective Synthesis of 1,4-Disubstituted 1,3-Diene from Aldehyde Using Organotitanium Reagent

Article abstract of DOI:10.1016/S0040-4020(01)90007-9

Organotitanium reagent generated from 1-t-butylthio-3-trimethylsilyl-1-propene condenses with aldehydes to give 1-t-butylthio-(E,Z)-1,3-alkadienes in a single step via (E)-erythro-β-hydroxysilane in a highly regio- and stereoselective manner. 1,4-Dialkyl-1,3-diene is obtained from the diene sulfide by crosscoupling reaction with Grignard reagent in the presence of nickel catalyst.The utility of the method is illustrated by application to the synthesis of Spilanthol, a naturally occurring insecticide from Spilanthese olerancae in five steps.