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Mild Ring‐Opening 1,3‐Hydroborations of Non‐Activated Cyclopropanes
Author(s) -
Wang Di,
Xue XiaoSong,
Houk Kendall N.,
Shi Zhuangzhi
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201811036
Subject(s) - markovnikov's rule , hydroboration , chemistry , ring (chemistry) , boron , cationic polymerization , silane , olefin fiber , medicinal chemistry , hydride , computational chemistry , organic chemistry , regioselectivity , catalysis , hydrogen
Abstract The Brown hydroboration reaction, first reported in 1957, is the addition of B−H across an olefin in an anti‐Markovnikov fashion. Here, we solved a long‐standing problem on mild 1,3‐hydroborations of non‐activated cyclopropanes. A three‐component system including cyclopropanes, boron halides, and hydrosilanes has been developed for borylative ring‐opening of cyclopropanes following the anti‐Markovnikov rule, under mild reaction conditions. Density functional theory (M06‐2X) calculations show that the preferred pathway involves a cationic boron intermediate which is quenched by hydride transfer from the silane.