Direct nucleophilic and electrophilic activation of alcohols using a unified boron-based organocatalyst scaffold

Organocatalytic strategies for the direct activation of hydroxy-containing compounds have paled in comparison to those applicable to carbonyl compounds. To this end, boronic acids have emerged as valuable catalysts for the functionalization of hydroxy groups in a mild and selective fashion. Distinct modes of activation in boronic acid-catalyzed transformations are often accomplished by vastly different catalytic species, complicating the design of broadly applicable catalyst classes. Herein, we report the use of benzoxazaborine as a general scaffold for the development of structurally related yet mechanistically divergent catalysts for the direct nucleophilic and electrophilic activation of alcohols under ambient conditions. The utility of these catalysts is demonstrated in the monophosphorylation of vicinal diols and the reductive deoxygenation of benzylic alcohols and ketones respectively. Mechanistic studies of both processes reveal the contrasting nature of key tetravalent boron intermediates in the two catalytic manifolds.