Stereodivergent synthesis of vicinal quaternary-quaternary stereocenters and bioactive hyperolactones

Haifeng Zheng, Yan Wang, Chaoran Xu, Xi Xu, Lili Lin, Xiaohua Liu () and Xiaoming Feng ()
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Haifeng Zheng: Sichuan University
Yan Wang: Sichuan University
Chaoran Xu: Sichuan University
Xi Xu: Sichuan University
Lili Lin: Sichuan University
Xiaohua Liu: Sichuan University
Xiaoming Feng: Sichuan University

Nature Communications, 2018, vol. 9, issue 1, 1-7

Abstract: 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.

Date: 2018
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DOI: 10.1038/s41467-018-04123-w

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