Identification of a key intermediate in the asymmetric Appel process: one pot stereoselective synthesis of P-stereogenic phosphines and phosphine boranes from racemic phosphine oxides

Abstract

Sequential treatment of racemic phosphine oxides with oxalyl chloride and chiral non-racemic alcohol generates the same ratios of diastereomeric alkoxyphosphonium salts obtained in the corresponding asymmetric Appel process, strongly implicating the intermediate chlorophosphonium salt in the stereoselecting step. Subsequent reduction allows a novel synthesis of enantioenriched P-stereogenic phosphines–phosphine boranes.