Reaktionen mit alkylidenephosphoranen—XVIII : Kinetische racematspaltungen durch umsetzung von alkylidenphosphoranen mit optisch aktiven säurechloriden

Abstract

The reaction of alkylidenephosphoranes with acyl chlorides proceeds by transylidation. Starting from an alkylidenephosphorane containing an chiral P-atom and an optical active acyl chloride, partial kinetic resolution of the organophosphorus compound is observed. The reaction of 1-carboethoxyethylidenenaphthylphenylmethylphosphorane with an optical active acyl chloride proceeds by simultaneous kinetic resolution and partial asymmetric synthesis of allenecarboxylic esters. Kinetic resolution is also observed in the reaction of carboalkoxymethylene-triphenylphosphoranes, containing a chiral centre in the ester function, with optical active acyl chlorides. Optical active alcohols are obtained after hydrolysis of the reaction products. The steric course of the reaction is discussed and the absolute configuration of several compounds are assigned.