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General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis

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Title: General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis
Authors: Shishido, Ryosuke Browse this author
Uesugi, Minami Browse this author
Takahashi, Rikuro Browse this author
Mita, Tsuyoshi Browse this author
Ishiyama, Tatsuo Browse this author →KAKEN DB
Kubota, Koji Browse this author
Ito, Hajime Browse this author →KAKEN DB
Keywords: Silylaton
Substitution reactions
Issue Date: 19-Aug-2020
Publisher: American Chemical Society
Journal Title: Journal of the American Chemical Society
Volume: 142
Issue: 33
Start Page: 14125
End Page: 14133
Publisher DOI: 10.1021/jacs.0c03011
Abstract: Compared to carbon-based nucleophiles, the number of silicon-based nucleophiles that is currently available remains limited, which significantly hampers the structural diversity of synthetically accessible silicon-based molecules. Given the high synthetic utility and ease of handling of carbon-based boron nucleophiles, silicon-based boron nucleophiles, i.e., silylboranes, have attracted considerable interest in recent years as nucleophilic silylation reagents that are activated by transition-metal catalysts or bases. However, the range of practically accessible silylboranes remains limited. In particular, the preparation of sterically hindered and functionalized silylboranes remains a significant challenge. Here, we report the use of rhodium and platinum catalysts for the direct borylation of hydrosilanes with bis(pinacolato)diboron, which allows the synthesis of new trialkylsilylboranes that bear bulky alkyl groups and functional groups as well as new dialkylarylsilylboranes that are difficult to synthesize via conventional methods using alkali metals. We further demonstrate that these compounds can be used as silicon nucleophiles in organic transformations, which significantly expands the scope of synthetically accessible organosilicon compounds compared to previously reported methods. Thus, the present study can be expected to inspire the development of efficient methods for novel silicon-containing bioactive molecules and organic materials with desirable properties. We also report the first B-11{H-1} and Si-29(H-1) NMR spectroscopic evidence for the formation of i-Pr3SiLi generated by the reaction of i-Pr3Si-B(pin) with MeLi.
Rights: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
Type: article (author version)
Appears in Collections:工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 久保田 浩司

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