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Dual-Hydrogen-Bond Donor and Brønsted Acid Cocatalysis Enables Highly Enantioselective Protio-Semipinacol Rearrangement Reactions.
Blackburn, Melanie A S; Wagen, Corin C; Bodrogean, M Raul; Tadross, Pamela M; Bendelsmith, Andrew J; Kutateladze, Dennis A; Jacobsen, Eric N.
Afiliação
  • Blackburn MAS; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
  • Wagen CC; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
  • Bodrogean MR; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
  • Tadross PM; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
  • Bendelsmith AJ; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
  • Kutateladze DA; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
  • Jacobsen EN; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
J Am Chem Soc ; 145(28): 15036-15042, 2023 Jul 19.
Article em En | MEDLINE | ID: mdl-37428959
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.

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2023 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2023 Tipo de documento: Article