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Published June 12, 2019 | Accepted Version + Submitted + Supplemental Material
Journal Article Open

Vinyl Carbocations Generated under Basic Conditions and Their Intramolecular C–H Insertion Reactions


Here we report the surprising discovery that high-energy vinyl carbocations can be generated under strongly basic conditions, and that they engage in intramolecular sp³ C–H insertion reactions through the catalysis of weakly coordinating anion salts. This approach relies on the unconventional combination of lithium hexamethyldisilazide base and the commercially available catalyst, triphenylmethylium tetrakis(pentafluorophenyl)borate. These reagents form a catalytically active lithium species that enables the application of vinyl cation C–H insertion reactions to heteroatom-containing substrates.

Additional Information

© 2019 American Chemical Society. Received 24 February 2019. Published online 13 May 2019. Published in issue 12 June 2019. Financial support for this work was generously provided by the David and Lucile Packard Foundation (to H.M.N.), the Alfred P. Sloan Foundation (to H.M.N.), the Pew Charitable Trusts (to H.M.N), the NIH-NIGMS (R35 GM128936 to H.M.N.), and the National Science Foundation (CHE-1764328 to K.N.H., CHE-1455348 to V.L., and DGE-1650604 to S.P. and B.W.). A.L.B. and B.W. thank the Christopher S. Foote Fellowship for funding. The authors thank the UCLA Molecular Instrumentation Center for NMR and mass spectroscopy instrumentation as well as the Mass Spectrometry facility at the University of California, Irvine. Computations were performed on the Hoffman2 cluster at UCLA and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the NSF (OCI-1053575). The authors declare no competing financial interest.

Attached Files

Accepted Version - nihms-1035920.pdf

Submitted - strong-bases-and-weak-anions-in-catalytic-c-h-insertion-reactions-of-vinyl-carbocations.pdf

Supplemental Material - ja9b02110_si_001.pdf


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August 19, 2023
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