α-Selective Ring-Opening Reactions of Bicyclo[1.1.0]butyl Boronic Ester with Nucleophiles

Abstract

The reaction of bicyclo[1.1.0]butyl pinacol boronic ester (BCB-Bpin) with nucleophiles has been studied. Unlike BCBs bearing electron-withdrawing groups, which react with nucleophiles at the β-position, BCB-Bpin reacts with a diverse set of heteroatom (O, S, N)-centred nucleophiles exclusively at the α-position. Aliphatic alcohols, phenols, carboxylic acids, thiols and sulfonamides were found to be competent nucleophiles, providing ready access to α-heteroatom-substituted cyclobutyl boronic esters. In contrast, sterically hindered bis-sulfonamides and related nucleophiles reacted with BCB-Bpin at the β'-position leading to cyclopropanes with high trans-selectivity. The origin of selectivity is discussed.

Keywords: 1,2-migration; boronic esters; cyclobutane; cyclopropane; strain release.