α-Selective Ring-Opening Reactions of Bicyclo[1.1.0]butyl Boronic Ester with Nucleophiles
Lin Guo
Bristol University, Department of Chemistry, Cantock's Close, Bristol, BS8 1TS UK
Search for more papers by this authorAdam Noble
Bristol University, Department of Chemistry, Cantock's Close, Bristol, BS8 1TS UK
Search for more papers by this authorCorresponding Author
Prof. Varinder K. Aggarwal
Bristol University, Department of Chemistry, Cantock's Close, Bristol, BS8 1TS UK
Search for more papers by this authorLin Guo
Bristol University, Department of Chemistry, Cantock's Close, Bristol, BS8 1TS UK
Search for more papers by this authorAdam Noble
Bristol University, Department of Chemistry, Cantock's Close, Bristol, BS8 1TS UK
Search for more papers by this authorCorresponding Author
Prof. Varinder K. Aggarwal
Bristol University, Department of Chemistry, Cantock's Close, Bristol, BS8 1TS UK
Search for more papers by this authorAbstract
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.
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