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Synfacts 2022; 18(04): 0345
DOI: 10.1055/s-0041-1737931
Synthesis of Natural Products and Potential Drugs

Syntheses of (–)-Crinipellins C and F

Contributor(s):
Erick M. Carreira
,
Viktoria C. Gerken
Zhao Y, Hu J, Chen R, Xiong F, Xie H, *, Ding H. * Zhejiang University and Zhejiang Gongshang University, Hangzhou, P. R. of China
Divergent Total Syntheses of (−)-Crinipellins Facilitated by a HAT-Initiated Dowd−Beckwith Rearrangement.

J. Am. Chem. Soc. 2022;
144: 2495-2500
DOI: 10.1021/jacs.1c13370.
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Key words

(–)-crinipellins - Stork–Danheiser transposition - [5+2] cycloaddition - Dowd–Beckwith rearrangement - Wilkinson hydrogenation

Significance

The crinipellins are highly oxygenated tetraquinane natural products. Ding, Xie, and co-workers present their total syntheses featuring a HAT-initiated Dowd–Beckwith rearrangement. With enone L as a common intermediate, the ­authors were able to access eight natural products of the crinipellin family.


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Comment

Cycloaddition precursor G was synthesized by Stork–Danheiser transposition of vinylogous ester E. An oxidative dearomatization-induced [5+2] cycloaddition pinacol rearrangement cascade yielded tetracycle H. Alkene I underwent a hydrogen atom transfer initiated Dowd–Beckwith rearrangement furnishing the tetraquinane framework.


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Publication History

Article published online:
18 March 2022

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