Enantioselective synthesis of 2,2-disubstituted terminal epoxides via catalytic asymmetric Corey-Chaykovsky epoxidation of ketones

Catalytic asymmetric Corey-Chaykovsky epoxidation of various ketones with dimethyloxosulfonium methylide using a heterobimetallic La-Li(3)-BINOL complex (LLB) is described. The reaction proceeded smoothly at room temperature in the presence of achiral phosphine oxide additives, and 2,2-disubstituted...

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Published inMolecules (Basel, Switzerland) Vol. 17; no. 2; pp. 1617 - 1634
Main Authors Sone, Toshihiko, Yamaguchi, Akitake, Matsunaga, Shigeki, Shibasaki, Masakatsu
Format Journal Article
LanguageEnglish
Published Switzerland MDPI AG 07.02.2012
MDPI
Subjects
Acids
asymmetric catalysis
asymmetric synthesis
Catalysis
epoxide
Epoxy Compounds - chemistry
Hypotheses
Ketones - chemistry
Magnetic Resonance Spectroscopy
rare earth metal
Spectrometry, Mass, Electrospray Ionization
Spectroscopy, Fourier Transform Infrared
Stereoisomerism
Sulfur
sulfur ylide
Japan
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Summary:Catalytic asymmetric Corey-Chaykovsky epoxidation of various ketones with dimethyloxosulfonium methylide using a heterobimetallic La-Li(3)-BINOL complex (LLB) is described. The reaction proceeded smoothly at room temperature in the presence of achiral phosphine oxide additives, and 2,2-disubstituted terminal epoxides were obtained in high enantioselectivity (97%-91% ee) and yield ( > 99%-88%) from a broad range of methyl ketones with 1-5 mol% catalyst loading. Enantioselectivity was strongly dependent on the steric hindrance, and other ketones, such as ethyl ketones and propyl ketones resulted in slightly lower enantioselectivity (88%-67% ee).
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ISSN:1420-3049
1420-3049
DOI:10.3390/molecules17021617