Chemoselective boronic ester synthesis via controlled speciation

Abstract

Control of boronic acid solution speciation is presented as a new strategy for the chemoselective synthesis of boronic esters. Manipulation of the solution equilibria within a cross-coupling milieu enables the formal homologation of aryl and alkenyl boronic acid pinacol esters. The generation of a new, reactive boronic ester in the presence of an active Pd catalyst also facilitates streamlined iterative catalytic C—C bond formation and provides a method for the controlled oligomerization of sp2-hybridized boronic esters.