An electrophilic cleavage procedure for the asymmetric dihydroxylation: direct enantioselective synthesis of cyclic boronic esters from olefins

Abstract

A variation within the osmium-catalysed asymmetric dihydroxylation (AD) of olefins is described that yields cyclic boronic esters from olefins in a straight-forward manner. This process represents the first real product alteration in asymmetric dihydroxylation, since all previous protocols lead to free diols exclusively. A protocol based on the Sharpless AD conditions (for enantioselective oxidation of prochiral olefins) was developed that gives cyclic boronic esters with excellent enantiomeric excesses (ee's). Some of the ee's are higher than those reported for conventional AD. The unprecedented role of phenyl boronic acid on the course of the AD reaction was investigated in detail. PhB(OH)2 does not interfere with the chiral ligand, leaving the enantioselective step of olefin oxidation intact. The main role of the boronic acids-apart from protecting the diol products against potential overoxidation-relies on removing the diol entity in an electrophilic cleavage, which is in contrast to the conventional hydrolytic cleavage of the AD protocols. Thus, a mechanistically new cleavage for enantioselective dihydroxylation reactions is introduced within the present work.