Ru-Catalyzed Geminal Hydroboration of Silyl Alkynes via a New gem -Addition Mechanism

Journal of the American Chemical Society
Qiang FengJianwei Sun

Abstract

While 1,2-addition represents the most common mode of alkyne hydroboration, herein we describe a new 1,1-hydroboration mode. It is the first demonstration of gem-(H,B) addition to an alkyne triple bond. With the superior [CpRu(MeCN)3]PF6 catalyst, a range of silyl alkynes reacted efficiently with HBpin under mild conditions to form various synthetically useful silyl vinyl boronates with complete stereoselectivity and broad functional group compatibility. An extension to germanyl alkynes and the hydrosilylation of alkynyl boronates toward the same type of products were also achieved. Mechanistically, this process features a new pathway featuring gem-(H,B) addition to form the key α-boryl-α-silyl Ru-carbene intermediate followed by silyl migration. It is believed that the orbital interaction between boron and Cβ in the coplanar relationship between the boron atom and the ruthenacyclopropene ring preceding boron migration is responsible for the new reactivity. Control experiments and DFT (including molecular dynamics) calculations provided important insights into the mechanism, which excluded the involvement of a metal vinylidene intermediate. This study represents a new step forward not only for alkyne hydroboration but also for ...Continue Reading

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Citations

Dec 12, 2020·Angewandte Chemie·Karel ŠkochGerhard Erker
May 25, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Yuichiro MutohShinichi Saito
Jul 10, 2021·Chemistry : a European Journal·Romain MelotAlois Fürstner
Nov 26, 2020·Journal of the American Chemical Society·Ji-Min YangQi-Lin Zhou
Dec 30, 2020·Journal of the American Chemical Society·Jianguo LiuWenguang Wang
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