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Synfacts 2018; 14(12): 1217
DOI: 10.1055/s-0037-1611130
Synthesis of Natural Products and Potential Drugs
© Georg Thieme Verlag Stuttgart · New York

Divergent Route to Gelsedine-Type Alkaloids

Contributor(s):
Erick M. Carreira
,
Niels Sievertsen
Wang P, Gao Y, Ma D. * Shanghai Institute of Organic Chemistry, P. R. of China
Divergent Entry to Gelsedine-Type Alkaloids: Total Syntheses of (–)-Gelsedilam, (–)-Gelsenicine, (–)-Gelsedine, and (–)-Gelsemoxonine.

J. Am. Chem. Soc. 2018;
140: 11608-11612
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Further Information

Publication History

Publication Date:
19 November 2018 (online)

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Key words

Gelsemium alkaloids - Michael addition - aldol cyclization - pinacol rearrangement

Significance

Gelsedine-type natural products have attracted considerable interest from the synthetic community owing to their interesting biological properties and complex architectures. Ma and co-workers have developed and executed an elegant synthetic route culminating in the preparation of four such alkaloids relying on an asymmetric Michael addition, tandem oxidation-aldol cyclization, and a pinacol rearrangement.


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Comment

Indole derivative B and enone E underwent conjugate addition to furnish F. Oxidation and aldol cyclization resulted in the formation of key structure G in a single pot. Cationic rearrangement of G provided the oxabicyclo[3.2.2]nonane skeleton present in all targets. (–)-Gelsedilam was synthesized from H in four steps. (–)-Gelsemoxonine, (–)-gelsenicine, and (–)-gelsedine were accessed via ethyl ketone J.


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