Main Group-Catalyzed Cationic Claisen Rearrangements via Vinyl Carbocations
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1.
California Institute of Technology
Abstract
We report a catalytic C–O coupling/Claisen cascade reaction enabled by interception of vinyl carbocations with allyl ethers. The reaction utilizes commercially available borate salts as catalysts and is effective at constructing sterically hindered C–C bonds. The reaction mechanism is studied experimentally and computationally to support a charge-accelerated [3,3] rearrangement of a silyloxonium cation. Our reaction is also applied to the highly stereoselective synthesis of fully substituted vinyl ethers.
Copyright and License
© 2024 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0.
Acknowledgement
Financial support for this work was provided by the National Institutes of Health National Institute of General Medical Sciences (R35 GM128936 to H.M.N.) and the National Science Foundation (CHE-1764328 to K.N.H.). The authors thank the Beckman Institute, Dr. Scott Virgil (Caltech) for instrumentation, and Dr. Mona Shahgholi (Caltech) for mass spectrometry support. Work by the Houk group used computational and storage services associated with the Hoffman2 Shared Cluster provided by UCLA Institute for Digital Research and Education’s Research Technology Group. Portions of this manuscript were adapted from Caltech thesis DOI: 10.7907/rkge-pz74.
Contributions
C.G.W. and S.K.N. contributed equally. This paper was written through contributions of C.G.W., S.K.N., K.D., W.L., and H.M.N. C.G.W., S.K.N., and K.D. carried out the experimental work. W.L. carried out the computational work. K.N.H. supervised the computational work. C.G.W., S.K.N., and H.M.N. conceived the project. All authors have given approval to the final version of the manuscript.
Data Availability
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Experimental procedures, characterization data, NMR spectra, and computational data (PDF)
Conflict of Interest
The authors declare no competing financial interest.
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Additional details
- ISSN
- 1523-7052
- DOI
- 10.1021/acs.orglett.4c00837
- PMCID
- PMC11187624
- National Institutes of Health
- R35 GM128936
- National Science Foundation
- CHE-1764328