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Asymmetric CuI-Catalyzed Insertion Reaction of 1-Aryl-2,2,2-trifluoro-1-diazoethanes into Si–H Bonds

Cite this: Org. Lett. 2019, 21, 22, 9094–9098
Publication Date (Web):October 28, 2019
https://doi.org/10.1021/acs.orglett.9b03480
Copyright © 2019 American Chemical Society
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    Abstract

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    An asymmetric copper(I)-catalyzed Si–H insertion reaction of 1-aryl-2,2,2-trifluoro-1-diazoethanes in dimethyl carbonate as a green solvent alternative was developed. A C2-symmetric copper(I) diimine complex enabled the asymmetric insertion reaction to give enantioenriched (1-aryl-2,2,2-trifluoroethyl)silanes with excellent stereoselectivities (up to 98:2 er). Successful conversion of the silanes into the corresponding alcohols was performed with retention of stereochemistry. Mechanistic studies and DFT calculations support the proposed model for the observed stereoselectivities.

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