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Electrochemical Fluorination of Vinyl Boronates through Donor-Stabilized Vinyl Carbocation Intermediates

Wigman, Benjamin and Lee, Woojin and Wei, Wenjing and Houk, Kendall N. and Nelson, Hosea M. (2022) Electrochemical Fluorination of Vinyl Boronates through Donor-Stabilized Vinyl Carbocation Intermediates. Angewandte Chemie International Edition, 61 (12). Art. No. e202113972. ISSN 1433-7851. PMCID PMC8901537. doi:10.1002/anie.202113972. https://resolver.caltech.edu/CaltechAUTHORS:20210921-223337255

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Abstract

The electrochemical generation of vinyl carbocations from alkenyl boronic esters and boronates is reported. Using easy-to-handle nucleophilic fluoride reagents, these intermediates are trapped to form fully substituted vinyl fluorides. Mechanistic studies support the formation of dicoordinated carbocations through sequential single-electron oxidation events. Notably, this electrochemical fluorination features fast reaction times and Lewis acid-free conditions. This transformation provides a complementary method to access vinyl fluorides with simple fluoride salts such as TBAF.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1002/anie.202113972DOIArticle
https://doi.org/10.33774/chemrxiv-2021-j5lrxDOIDiscussion Paper
ORCID:
AuthorORCID
Wigman, Benjamin0000-0003-3689-8281
Lee, Woojin0000-0002-8531-0301
Houk, Kendall N.0000-0002-8387-5261
Nelson, Hosea M.0000-0002-4666-2793
Additional Information:© 2022 Wiley-VCH GmbH. Issue Online: 07 March 2022; Version of Record online: 03 February 2022; Accepted manuscript online: 14 January 2022; Manuscript received: 14 October 2021. Financial support for this work was generously provided by the Alfred P. Sloan Foundation (to H.M.N.), the NIH-NIGMS (R35GM128936 to H.M.N.), and the National Science Foundation (CHE-1764328 to K.N.H and DGE-1650604 to B.W.). B.W. thanks the Christopher S. Foote Fellowship for funding. The authors thank the Mass Spectrometry facility at the University of California, Irvine. Computations were performed on the Hoffman2 cluster at UCLA. Cyclic voltammetry was performed in the laboratory of Prof. Chong Liu with Benjamin Natinsky. Finally, we thank Prof. Song Lin and Juno Siu for useful discussions. The authors declare no conflict of interest.
Funders:
Funding AgencyGrant Number
Alfred P. Sloan FoundationUNSPECIFIED
NIHR35 GM128936
NSFCHE-1764328
NSF Graduate Research FellowshipDGE-1650604
UCLAUNSPECIFIED
Subject Keywords:Alkenyl Boronates; Electrochemistry; Fluorination; Vinyl Carbocations; Vinyl Fluorides
Issue or Number:12
PubMed Central ID:PMC8901537
DOI:10.1002/anie.202113972
Record Number:CaltechAUTHORS:20210921-223337255
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210921-223337255
Official Citation:Electrochemical Fluorination of Vinyl Boronates through Donor-Stabilized Vinyl Carbocation Intermediates. B. Wigman, W. Lee, W. Wei, K. N. Houk, H. M. Nelson, Angew. Chem. Int. Ed. 2022, 61, e202113972; Angew. Chem. 2022, 134, e202113972; DOI: 10.1002/anie.202113972
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:110980
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:21 Sep 2021 23:29
Last Modified:06 May 2022 16:31

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