Carbene-Catalyzed Enantioselective Decarboxylative Annulations to Access Dihydrobenzoxazinones and Quinolones

Ansoo Lee, Joshua L. Zhu, Taisiia Feoktistova, Alexander C. Brueckner, Paul H.Y. Cheong*, Karl A. Scheidt

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

21 Scopus citations

Abstract

A direct decarboxylative strategy for the generation of aza-o-quinone methides (aza-o-QMs) by N-heterocyclic carbene (NHC) catalysis has been discovered and explored. This process requires no stoichiometric additives in contrast with current approaches. Aza-o-QMs react with trifluoromethyl ketones through a formal [4+2] manifold to access highly enantioenriched dihydrobenzoxazin-4-one products, which can be converted to dihydroquinolones through an interesting stereoretentive aza-Petasis–Ferrier rearrangement sequence. Complementary dispersion-corrected density functional theory (DFT) studies provided an accurate prediction of the reaction enantioselectivity and lend further insight to the origins of stereocontrol. Additionally, a computed potential energy surface around the major transition structure suggests a concerted asynchronous mechanism for the formal annulation.

Original languageEnglish (US)
Pages (from-to)5941-5945
Number of pages5
JournalAngewandte Chemie - International Edition
Volume58
Issue number18
DOIs
StatePublished - Apr 23 2019

Keywords

  • N-heterocyclic carbenes
  • annulation
  • asymmetric synthesis
  • homogeneous catalysis
  • organocatalysis

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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