CuH-Catalyzed Regio- and Enantioselective Formal Hydroformylation of Vinyl Arenes
Name
nihms-2011741.pdf
Description
Accepted version
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1.15 MB
Format
Adobe PDF
Checksum (MD5)
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Author(s)
Garhwal, Subhash
Dong, Yuyang
Mai, Binh Khanh
Liu, Peng
Buchwald, Stephen L
Date Issued
May 9, 2024
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Citation
CuH-Catalyzed Regio- and Enantioselective Formal Hydroformylation of Vinyl Arenes. Subhash Garhwal, Yuyang Dong, Binh Khanh Mai, Peng Liu, and Stephen L. Buchwald. Journal of the American Chemical Society 2024 146 (20), 13733-13740.
Version
Author's final manuscript
Abstract
A highly enantioselective formal hydroformylation of vinyl arenes enabled by copper hydride (CuH) catalysis is reported. Key to the success of the method was the use of the mild Lewis acid zinc triflate to promote the formation of oxocarbenium electrophiles through the activation of diethoxymethyl acetate. Using the newly developed protocol, a broad range of vinyl arene substrates underwent efficient hydroacetalization reactions to provide access to highly enantioenriched α-aryl acetal products in good yields with exclusively branched regioselectivity. The acetal products could be converted to the corresponding aldehydes, alcohols, and amines with full preservation of the enantiomeric purity. Density functional theory studies support that the key C–C bond-forming event between the alkyl copper intermediate and the oxocarbenium electrophile takes place with inversion of configuration of the Cu–C bond in a backside SE2-type mechanism.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
10.1021/jacs.4c04287
