Dual-Hydrogen-Bond Donor and Brønsted Acid Cocatalysis Enables Highly Enantioselective Protio-Semipinacol Rearrangement Reactions

Dual-Hydrogen-Bond Donor and Brønsted Acid Cocatalysis Enables Highly Enantioselective Protio-Semipinacol Rearrangement Reactions

A catalytic protio-semipinacol ring-expansion reaction has been developed for the highly enantioselective conversion of tertiary vinylic cyclopropyl alcohols into cyclobutanone products bearing α-quaternary stereogenic centers. The method relies on the cocatalytic effect of a chiral dual-hydrogen-bo...

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Veröffentlicht in:Journal of the American Chemical Society 2023-07, Vol.145 (28), p.15036-15042
Hauptverfasser: Blackburn, Melanie A. S., Wagen, Corin C., Bodrogean, M. Raul, Tadross, Pamela M., Bendelsmith, Andrew J., Kutateladze, Dennis A., Jacobsen, Eric N.
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container_end_page 15042
container_issue 28
container_start_page 15036
container_title Journal of the American Chemical Society
container_volume 145
creator Blackburn, Melanie A. S.
Wagen, Corin C.
Bodrogean, M. Raul
Tadross, Pamela M.
Bendelsmith, Andrew J.
Kutateladze, Dennis A.
Jacobsen, Eric N.
description A catalytic protio-semipinacol ring-expansion reaction has been developed for the highly enantioselective conversion of tertiary vinylic cyclopropyl alcohols into cyclobutanone products bearing α-quaternary stereogenic centers. The method relies on the cocatalytic effect of a chiral dual-hydrogen-bond donor (HBD) with hydrogen chloride. Experimental evidence is provided for a stepwise mechanism where protonation of the alkene generates a short-lived, high-energy carbocation, which is followed by C–C bond migration to deliver the enantioenriched product. This research applies strong acid/chiral HBD cocatalysis to weakly basic olefinic substrates and lays the foundation for further investigations of enantioselective reactions involving high-energy cationic intermediates.
doi_str_mv 10.1021/jacs.3c02960
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title Dual-Hydrogen-Bond Donor and Brønsted Acid Cocatalysis Enables Highly Enantioselective Protio-Semipinacol Rearrangement Reactions
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