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Design, Synthesis, and Implementation of Sodium Silylsilanolates as Silyl Transfer Reagent

preprint
revised on 27.05.2021, 10:39 and posted on 28.05.2021, 08:14 by Hiroki Yamagishi, Hayate Saito, Jun Shimokawa, Hideki Yorimitsu
There is an increasing demand for facile delivery of silyl groups onto organic bioactive molecules. One of the common methods of silylation via a transition metal-catalyzed coupling reaction employs hydrosilane, disilane, and silylborane as major silicon sources. However, labile nature of the reagents or harsh reaction conditions sometimes renders them inadequate for the purpose. Thus, a more versatile alternative source of silyl groups has been desired. We hereby report a design, synthesis, and implementation of new storable sodium silylsilanolates that can be used for the silylation of aryl halides and pseudohalides in the presence of a palladium catalyst. The new method allows a late-stage functionalization of polyfunctionalized compounds with a variety of silyl groups. Mechanistic studies indicate that 1) a nucleophilic silanolate attacks a palladium center to afford a silylsilanolate-coordinated arylpalladium intermediate and 2) a polymeric cluster of silanolate species assists in the intramolecular migration of silyl groups, which would pro-mote an efficient transmetalation.

Funding

Development and utilization of a new silyl metal precursor disilanolate

Japan Society for the Promotion of Science

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Organic synthesis by means of breaking aromaticity via reduction

Japan Society for the Promotion of Science

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Development of new synthesis method of boracycle using transition metal catalyst

Japan Society for the Promotion of Science

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Creation of advanced functionalization method based on electron injection into unsaturated bond

Japan Science and Technology Agency

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KAKENHI (Grant No. 21H01934) from the Japan Society for the Promotion of Science (JSPS)

History

Email Address of Submitting Author

shimokawa@kuchem.kyoto-u.ac.jp

Institution

Kyoto University

Country

Japan

ORCID For Submitting Author

0000-0002-4023-4640

Declaration of Conflict of Interest

The authors declare no conflict of interest.

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