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Enantioselective Hydroamination of Alkenes with Sulfonamides Enabled by Proton-Coupled Electron Transfer

preprint
submitted on 04.02.2020 and posted on 04.02.2020 by Casey B. Roos, Joachim Demaerel, David E. Graff, Robert Knowles

An enantioselective, radical-based method for the intramolecular hydroamination of alkenes with sulfonamides is reported. These reactions are proposed to proceed via N-centered radicals formed by proton-coupled electron transfer (PCET) activation of sulfonamide N–H bonds. Non-covalent interactions between the neutral sulfonamidyl radical and a chiral phosphoric acid generated in the PCET event are hypothesized to serve as the basis for asymmetric induction in a subsequent C–N bond forming step, achieving selectivities of up to 98:2 er. These results offer further support for the ability of non-covalent interactions to enforce stereoselectivity in reactions of transient and highly reactive open-shell intermediates.

Funding

NIH NIGMS R35 GM134893

Research Foundation ­ Flanders (FWO) Fundamental Research Fellowship 11ZY118N (to J.D.)

History

Email Address of Submitting Author

rknowles@princeton.edu

Institution

Princeton University

Country

USA

ORCID For Submitting Author

0000-0003-1044-4900

Declaration of Conflict of Interest

No conflict of interest

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