In Situ Generation of Silylzinc by Si−B Bond Activation Enabling Silylzincation and Silaboration of Terminal Alkynes

A new protocol has been designed for the in situ generation of unstable Si−Zn species through the reaction of dialkylzinc, phosphine, and silylborane (Si−B). Successive reactions with various terminal alkynes using this protocol enabled highly controllable regio‐/stereo‐/chemoselective silylzincatio...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-07, Vol.57 (27), p.8053-8057
Main Authors: Nagashima, Yuki, Yukimori, Daiki, Wang, Chao, Uchiyama, Masanobu
Format: Article
Language:English
Subjects:
Alkynes
boranes
Phosphine
silicon
synthetic methods
Zinc
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Summary:A new protocol has been designed for the in situ generation of unstable Si−Zn species through the reaction of dialkylzinc, phosphine, and silylborane (Si−B). Successive reactions with various terminal alkynes using this protocol enabled highly controllable regio‐/stereo‐/chemoselective silylzincation and silaboration on demand without the need for a transition‐metal catalyst. On demand: The in situ generation of silylzinc species was achieved by reacting dialkylzinc, phosphine, and silylborane. DFT calculations indicated that Si−B bond cleavage would afford the Si−Zn species. By using this protocol, successive reaction with various terminal alkynes enabled highly controllable regio‐/stereo‐/chemoselective silylzincation and silaboration of terminal alkynes on demand, thus affording synthetically versatile and densely functionalized vinylsilane and vinylboron derivatives.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201802887