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Selective Formal Carbene Insertion into Carbon-Boron Bonds of Diboronates by N-Trisylhydrazones |
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| Authors: | Zhicheng Bao Meirong Huang Prof. Dr. Yan Xu Prof. Dr. Xinhao Zhang Prof. Dr. Yun-Dong Wu Prof. Dr. Jianbo Wang |
| Affiliation: | 1. Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871 China These authors contributed equally to this work.;2. Shenzhen Bay Laboratory, Shenzhen, 518132 P. R. China Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, Peking University Shenzhen Graduate School, Shenzhen, 518055 P. R. China These authors contributed equally to this work.;3. Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871 China;4. Shenzhen Bay Laboratory, Shenzhen, 518132 P. R. China |
| Abstract: | Bisborylalkanes play important roles in organic synthesis as versatile bifunctional reagents. The two boron moieties in these compounds can be selectively converted into other functional groups through cross-coupling, oxidation or radical reactions. Thus, the development of efficient methods for synthesizing bisborylalkanes is highly demanded. Herein we report a new strategy to access bisborylalkanes through the reaction of N-trisylhydrazones with diboronate, in which the bis(boryl) methane is transformed into 1,2-bis(boronates) via formal carbene insertion. Since the N-trisylhydrazones can be readily derived from the corresponding aldehydes, this strategy represents a practical synthesis of 1,2-diboronates with broad substrate scope. Mechanistic studies reveal an unusual neighboring group effect of 1,1-bis(boronates), which accounts for the observed regioselectivity when unsymmetric 1,1-diboronates are applied. |
| Keywords: | 1,2-Boronates Boron Diazo Compound Regioselectivity 1,2-Shift |