A highly efficient procedure for hydroformylation and hydroamino-vinylation of methyl acrylate

Abstract

Methyl acrylate has been hydroformylated to the branched aldehyde with essentially perfect regio-selectivity and extraordinarily high average turnover frequencies (up to 4000 h–1). Using 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane based Rh catalyst with a substrate to catalyst ratio of 10 000, hydroformylation in excellent yield was achieved with complete branched selectivity in around 2 h. Performing this reaction in the presence of aromatic amines gave very high yields of the corresponding enamines in a quick one pot domino hydroaminovinylation reaction. Remarkably, this latter reaction works best under solvent-free conditions.