Metal-free C(aryl)–P bond cleavage: experimental and computational studies of the Michael addition/aryl migration of triarylphosphines to alkynyl esters

Abstract

The nucleophilic addition and aryl migration of triarylphosphines to alkynyl esters in the presence of water results in the formation of 3-(diarylphosphoryl)-3-aryl propanoic acid derivatives through a metal-free C(aryl)–P bond cleavage process. Experimental and computational investigations of the mechanism indicate that the rapid formation of hydroxy-λ⁵-phosphane as a key intermediate plays a crucial role in smooth C(aryl)–P bond cleavage.