Enantioselective Acyl Migration Reactions of Furanyl Carbonates with Chiral DMAP Derivatives

Kazuki Fujii, Koichi Mitsudo, Hiroki Mandai, Toshinobu Korenaga, Seiji Suga

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

An efficient enantioselective acyl migration reaction of furanyl carbonates was developed to construct all-carbon quaternary stereogenic centers. In some cases, the reactions required only 0.05 mol % (minimum 500 ppm) of catalyst and showed a high turnover frequency value (TOF; 3640 h−1). Multigram-scale reactions (10 grams) also proceeded with high enantioselectivity (>99:1 e.r.) in quantitative yield. The catalyst was robust and easily recovered in 98 % yield. A wide range of functional groups were tolerated (15 examples, >98 % yield, up to >99:1 e.r.), and a variety of optically active 3,3′-disubstituted benzofuranone derivatives, which are useful intermediates for the synthesis of natural products and pharmaceuticals, were efficiently obtained. Control experiments on the catalyst structure (e.g., catalyst 1 a vs. 1 a′ and 1 a′′) and computational calculations revealed that both the catalytic activity and enantioselectivity should be enhanced by hydrogen bonding between catalyst and substrate. Moreover, this system was applied to the challenging γ-selective acyl migration reaction of furanyl carbonates with high γ-selectivity and high enantioselectivity (α:γ=10:90, 95:5 e.r.).

Original languageEnglish
JournalChemistry - A European Journal
DOIs
Publication statusAccepted/In press - Jan 1 2019

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Carbonates
Enantioselectivity
Derivatives
Catalysts
Biological Products
Drug products
Functional groups
Catalyst activity
Hydrogen bonds
Carbon
Substrates
Pharmaceutical Preparations
Experiments

Keywords

  • acyl migration
  • DMAP derivative
  • enantioselectivity
  • organocatalysis
  • quaternary stereogenic center

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Cite this

Enantioselective Acyl Migration Reactions of Furanyl Carbonates with Chiral DMAP Derivatives. / Fujii, Kazuki; Mitsudo, Koichi; Mandai, Hiroki; Korenaga, Toshinobu; Suga, Seiji.

In: Chemistry - A European Journal, 01.01.2019.

Research output: Contribution to journalArticle

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