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Probing enantioselectivity in rhodium-catalyzed Si–C bond cleavage to construct silicon-stereocenters: a theoretical study

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Abstract

The rhodium-catalyzed asymmetric synthesis of dibenzooxasilines developed by Hayashi and co-workers provides an efficient method to construct tetraorganosilicon stereocenters. In the present study, density functional theory (DFT) calculations were performed to investigate the mechanism and enantioselectivity of this reaction. Theoretical calculations indicate that the mechanism involves the initial formation of an aryloxorhodium complex followed by Rh–Si exchange to afford an arylrhodium complex. The favorable oxidative addition/reductive elimination to cleave one Si–C(phenyl) bond from the arylrhodium complex determines the enantioselectivity. The enantioselectivity originates from the silyl moiety extruding from the phenyl ring on the rhodium atom in the reductive elimination transition state.

Graphical abstract: Probing enantioselectivity in rhodium-catalyzed Si–C bond cleavage to construct silicon-stereocenters: a theoretical study

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Publication details

The article was received on 01 Nov 2018, accepted on 13 Dec 2018 and first published on 14 Dec 2018


Article type: Paper
DOI: 10.1039/C8CY02261E
Citation: Catal. Sci. Technol., 2019, Advance Article
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    Probing enantioselectivity in rhodium-catalyzed Si–C bond cleavage to construct silicon-stereocenters: a theoretical study

    Z. Yu, T. Zhang, R. Bai and Y. Lan, Catal. Sci. Technol., 2019, Advance Article , DOI: 10.1039/C8CY02261E

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