Transition-metal- and solvent-free regioselective hydrosilylation of alkenes and allenes enabled by catalytic sodium tert-butoxide

Saini, S and Gupta, DK and Bhawar, R and Siddiqui, S and Mane, MV and Bose, SK (2023) Transition-metal- and solvent-free regioselective hydrosilylation of alkenes and allenes enabled by catalytic sodium tert-butoxide. In: Green Chemistry, 25 (23). pp. 10072-10081.

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Abstract

β-Selective hydrosilylation products of alkenes are of industrial importance, and the development of methods with Markovnikov selectivity is a growing area of research and still relatively rare. Herein, we have developed a convenient, transition-metal- and solvent-free method involving the alkali metal Lewis base NaOtBu as a catalyst and diphenyl silane (Ph2SiH2) as a silane reagent for the regioselective Markovnikov hydrosilylation of vinyl arenes and aliphatic alkenes in high yields with good functional group compatibility. Importantly, the hydrosilylation of allenes with Ph2SiH2 proceeds in a regioselective manner to afford (E)-allylsilane products. The utilization of the Earth-abundant sodium cation as a catalyst for hydrosilylation reactions appears to be unprecedented. We postulated the formation of a pentacoordinate silicon �ate� intermediate as evidenced by IR and mass spectrometry. Radical clock and trapping experiments support a radical mediated catalytic process. © 2023 The Royal Society of Chemistry.

Item Type:	Journal Article
Publication:	Green Chemistry
Publisher:	Royal Society of Chemistry
Additional Information:	The copyright for this article belongs to authors.
Keywords:	Catalysts; Industrial research; Mass spectrometry; Olefins; Regioselectivity; Silicon; Sodium compounds; Transition metals, Allenes; Hydrosilylations; Lewis base; Markovnikov selectivity; Metal free; Regio-selective; Solvent free; Solvent-free method; Tert-butoxide; ]+ catalyst, Hydrosilylation
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	29 Feb 2024 06:18
Last Modified:	29 Feb 2024 06:18
URI:	https://eprints.iisc.ac.in/id/eprint/83740

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