Bage Andrew D, Hunt Thomas A, Thomas Stephen P
EaStCHEM School of Chemistry, University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, United Kingdom.
Medicinal Chemistry, Early Oncology, AstraZeneca, Unit 310, Cambridge Science Park, Milton Road, Cambridge CB4 0WG, United Kingdom.
Org Lett. 2020 Jun 5;22(11):4107-4112. doi: 10.1021/acs.orglett.0c01168. Epub 2020 May 7.
Simple nucleophiles with structural similarities to known hydroboration catalysts can readily mediate the formation of BH and borohydride species from pinacolborane (HBpin). Alkyne and alkene hydroboration reactions were successfully mediated by nucleophiles through BH generation, with BH-catalyzed hydroboration found to dominate catalysis. NMR spectroscopy and kinetic analyses showed that the nucleophiles NaOBu, Na[N(SiMe)], BuMg, and BuLi only promoted the formation of BH and were not "true" hydroboration catalysts.
与已知硼氢化催化剂结构相似的简单亲核试剂能够轻易地介导由频哪醇硼烷（HBpin）形成BH和硼氢化物物种。亲核试剂通过BH的生成成功介导了炔烃和烯烃的硼氢化反应，发现BH催化的硼氢化反应在催化过程中占主导地位。核磁共振光谱和动力学分析表明，亲核试剂叔丁醇钠、Na[N(SiMe)]、丁基溴化镁和丁基锂仅促进BH的形成，并非“真正的”硼氢化催化剂。
