A Pd-catalyzed highly selective three-component protocol for trisubstituted allenes

Abstract

Herein we report the first example of a Pd-catalyzed highly selective three-component reaction of alkynyl-1,4-diol dicarbonates, organoboronic acids, and malonate anions for the efficient synthesis of trisubstituted 2,3-allenyl malonates not readily available by the known protocols. The reaction demonstrates an excellent regio- and chemo-selectivity for both the oxidative addition referring to the two C–O bonds and the subsequent coupling with the nucleophile with a remarkable functional group compatibility. A series of control experiments confirm a unique mechanism involving β-O elimination forming alka-1,2,3-triene and the subsequent insertion of its terminal CC bond into the Ar–Pd bond.