Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature

Abstract

An environmentally benign method for the transformation of allylic alcohols into carbonyl compounds is described. Using [Rh(COD(CH3CN)2]BF4 (2) in combination with 1,3,5-triaza-7-phosphaadamantane (PTA, 1) as the catalytic system in water results in a very fast redox isomerisation of a variety of secondary allylic alcohols at ambient temperature. Also, some primary allylic alcohols can be isomerised into the corresponding aldehydes. The active complex, which in some cases can be used in catalyst loadings as low as 0.5 mol%, is formed in situ from commercially available reagents. Based on deuterium labelling studies, a tentative mechanism involving metal-enone intermediates is presented.