Asymmetric synthesis of (−)-solanidine and (−)-tomatidenol

Yun Wang; Guanxin Huang; Yong Shi; Wei-sheng Tian; Chunlin Zhuang; Fen-Er Chen

doi:10.1039/D0OB00457J

Asymmetric synthesis of (−)-solanidine and (−)-tomatidenol†

Yun Wang,^ab Guanxin Huang,^a Yong Shi,

^c Wei-sheng Tian,^c Chunlin Zhuang

*^ab and Fen-Er Chen

*^abd

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* Corresponding authors

^a Engineering Center of Catalysis and Synthesis for Chiral Molecules, Fudan University, Shanghai 200433, China
E-mail: rfchen@fudan.edu.cn, zclnathan@163.com

^b Shanghai Engineering Center of Industrial Asymmetric Catalysis for Chiral Drugs, Shanghai 200433, China

^c Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China

^d Institute of Pharmaceutical Science and Technology, Zhejiang University of Technology, 18 Chao Wang Road, Hangzhou, China

Abstract

A concise asymmetric synthesis of two naturally occurring seco-type cholestane alkaloids (−)-solanidine and (−)-tomatidenol from (−)-diosgenin with a linear reaction sequence of 12 steps and 13 steps, respectively, is reported. The synthetic strategy includes the highly controlled establishment of highly functionalized octahydroindolizine ((−)-solanidine) and 1-oxa-6-azaspiro[4.5]decane ((−)-tomatidenol) cores with five stereocenters, respectively, from (−)-diosgenin, featuring two stereoselective cascade transformations including a modified cascade ring-switching process of furostan-26-acid to open the E-ring of (−)-diosgenin and a cascade azide reduction/intramolecular reductive amination to close the E- and F-rings of (−)-solanidine and (−)-tomatidenol. This work should enable further explorations of chemical and biological spaces based on solanidine, tomatidenol and related natural products.

This article is part of the themed collection: Total synthesis in OBC

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DOI: https://doi.org/10.1039/D0OB00457J
Article type: Paper
Submitted: 03 Mar 2020
Accepted: 01 Apr 2020
First published: 02 Apr 2020

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Org. Biomol. Chem., 2020,18, 3169-3176

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Asymmetric synthesis of (−)-solanidine and (−)-tomatidenol

Y. Wang, G. Huang, Y. Shi, W. Tian, C. Zhuang and F. Chen, Org. Biomol. Chem., 2020, 18, 3169 DOI: 10.1039/D0OB00457J

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Organic & Biomolecular Chemistry

Asymmetric synthesis of (−)-solanidine and (−)-tomatidenol†

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Asymmetric synthesis of (−)-solanidine and (−)-tomatidenol

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