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.
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| 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. | ||||||||||||
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| 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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