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

Virginie Carreras; Claire Besnard; Vincent Gandon; Thierry Ollevier

doi:10.1021/acs.orglett.9b03480

Asymmetric Cu^I-Catalyzed Insertion Reaction of 1-Aryl-2,2,2-trifluoro-1-diazoethanes into Si-H Bonds

Org Lett. 2019 Nov 15;21(22):9094-9098. doi: 10.1021/acs.orglett.9b03480. Epub 2019 Oct 28.

Authors

Virginie Carreras¹, Claire Besnard¹, Vincent Gandon^{2

3}, Thierry Ollevier¹

Affiliations

¹ Département de Chimie, Pavillon Alexandre-Vachon , Université Laval , 1045 avenue de la Médecine , Québec, QC , G1V 0A6 , Canada.
² ICMMO, CNRS UMR 8182, and Laboratoire de Chimie Moléculaire (LCM), CNRS UMR 9168 , Univ. Paris-Sud, Université Paris-Saclay , bâtiment 420 , 91405 Orsay Cedex, France.
³ Institut Polytechnique de Paris , École Polytechnique , route de Saclay , 91128 Palaiseau Cedex, France.

PMID: 31657938
DOI: 10.1021/acs.orglett.9b03480

Abstract

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.