Radical trans-Hydroboration of Alkynes with N-Heterocyclic Carbene Boranes

被引：92

作者：

Shimoi, Masaki ^{[1
]}

Watanabe, Takashi ^{[2
]}

Maeda, Katsuhiro ^{[1
,3
]}

Curran, Dennis P. ^{[4
]}

Taniguchi, Tsuyoshi ^{[1
,2
]}

机构：

[1] Kanazawa Univ, Grad Sch Nat Sci & Technol, Kakuma Machi, Kanazawa, Ishikawa 9201192, Japan

[2] Kanazawa Univ, Sch Pharmaceut Sci, Inst Med Pharmaceut & Hlth Sci, Kakuma Machi, Kanazawa, Ishikawa 9201192, Japan

[3] Kanazawa Univ, Nano Life Sci Inst WPI NanoLSI, Kakuma Machi, Kanazawa, Ishikawa 9201192, Japan

[4] Univ Pittsburgh, Dept Chem, Pittsburgh, PA 15260 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 30期

基金：

美国国家科学基金会;

关键词：

alkynes; carbenes; hydroboration; radical reactions; synthetic methods; CROSS-COUPLING REACTIONS; TERMINAL ALKYNES; SELECTIVE HYDROBORATION; INTERNAL ALKYNES; ALKENES; COMPLEXES;

D O I：

10.1002/anie.201804515

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Hydroboration of internal alkynes with N-heterocyclic carbene boranes (NHC-boranes) occurs to provide stable NHC (E)-alkenylboranes upon thermolysis in the presence of di-tert-butyl peroxide. The Eisomer results from an unusual trans-hydroboration, and the E/Z selectivity is typically high (90:10 or greater). Evidence suggests that this hydroboration occurs by a radical-chain reaction involving addition of an NHC-boryl radical to an alkyne to give a beta-NHC-borylalkenyl radical. Ensuing hydrogen abstraction from the starting NHC-borane provides the product and returns the starting NHC-boryl radical. Experiments suggest that the observed trans-selectivity results from kinetic control in the hydrogen-transfer reaction.

引用

页码：9485 / 9490

页数：6

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