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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, K. N. and Nelson, Hosea M. (2021) Electrochemical Fluorination of Vinyl Boronates Through Donor-Stabilized Vinyl Carbocation Intermediates. . (Unpublished) https://resolver.caltech.edu/CaltechAUTHORS:20210921-223337255

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Abstract

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


Item Type:Report or Paper (Discussion Paper)
Related URLs:
URLURL TypeDescription
https://doi.org/10.33774/chemrxiv-2021-j5lrxDOIDiscussion Paper
ORCID:
AuthorORCID
Houk, K. N.0000-0002-8387-5261
Nelson, Hosea M.0000-0002-4666-2793
Additional Information:The content is available under CC BY NC ND 4.0 License. Aug 19, 2021 Version 1. Financial support for this work was generously provided by the Alfred P. Sloan Foundation (to H.M.N.), the NIH-NIGMS (R35 GM128936 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. Author Contributions: The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. The author(s) have declared they have no conflict of interest with regard to this content. The author(s) have declared ethics committee/IRB approval is not relevant to this content.
Funders:
Funding AgencyGrant Number
Alfred P. Sloan FoundationUNSPECIFIED
NIHR35 GM128936
NSFCHE-1764328
NSF Graduate Research FellowshipDGE-1650604
UCLAUNSPECIFIED
Subject Keywords:electrochemistry; radical-polar crossover; fluorination; nucleophilic fluorination; vinyl carbocation; carbocation
DOI:10.33774/chemrxiv-2021-j5lrx
Record Number:CaltechAUTHORS:20210921-223337255
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210921-223337255
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:16 Nov 2021 19:43

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