Stereodivergent synthesis of vicinal quaternary-quaternary stereocenters and bioactive hyperolactones

Nature Communications
Haifeng ZhengXiaoming Feng

Abstract

Although great success has been achieved in asymmetric Claisen rearrangement for the synthesis of chiral γ,δ-unsaturated carbonyl compounds bearing vicinal tertiary-quaternary stereocenters, the development of asymmetric versions for stereodivergent construction of adjacent quaternary-quaternary stereocenters remains a formidable challenge because of the high steric hindrance. Here we report a catalytic enantioselective dearomatization Claisen rearrangement of allyl furyl ethers catalyzed by chiral N,N'-dioxide-NiII complex catalysts. A variety of chiral γ,δ-unsaturated carbonyl compounds bearing vicinal quaternary-quaternary stereocenters were obtained with excellent outcomes under mild conditions. Furthermore, we disclosed that by matching the configuration of the catalysts and the alkene unit of the substrates, four stereoisomers of the products could be prepared in excellent yields and stereoselectivities. Finally, the fascination of this strategy was demonstrated by stereodivergent synthesis of bioactive natural products hyperolactones B, C, and their epimers. A possible catalytic model was proposed to explain the origin of the asymmetric induction.

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Citations

Feb 12, 2019·Angewandte Chemie·Caroline ApelMathias Christmann
Jan 28, 2020·Chemical Communications : Chem Comm·Abigail R HanbyDavid R Spring
Jul 30, 2020·Chemical Communications : Chem Comm·Wei YangXiaoming Feng
Mar 18, 2020·Journal of the American Chemical Society·Javier MiróF Dean Toste
Nov 19, 2020·Journal of the American Chemical Society·Hanbyul KimSeunghoon Shin
Apr 23, 2020·Accounts of Chemical Research·Liang WeiChun-Jiang Wang

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Methods Mentioned

BETA
X-ray
circular dichroism
column chromatography

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