Chemoenzymatic synthesis of the cardenolide rhodexin A and its aglycone sarmentogenin

  • Beilstein J Org Chem. 2025 Dec 3:21:2637-2644. doi: 10.3762/bjoc.21.204.
Fuzhen Song  1 ,  Mengmeng Zheng  2 ,  Dongkai Wang  1 ,  Xudong Qu  3 ,  Qianghui Zhou  1
Affiliations
  • 1. Engineering Research Center of Organosilicon Compounds & Materials (Ministry of Education), Hubei Key Lab on Organic and Polymeric OptoElectronic Materials, College of Chemistry and Molecular Sciences, The Institute for Advanced Studies, TaiKang Center for Life and Medical Sciences and State Key Laboratory of Metabolism and Regulation in Complex Organisms, Wuhan University, Wuhan, 430072, China.
  • 2. School of Life Sciences, Shanghai University, Shanghai, 200444, China.
  • 3. State Key Laboratory of Microbial Metabolism and School of Life Sciences and Biotechnology, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, 200240, China.
PMID: 41367638 DOI: 10.3762/bjoc.21.204
Abstract

Herein, we report a concise chemoenzymatic synthesis of the cardenolide rhodexin A in 9 steps and the first protecting-group-free synthesis of its aglycone sarmentogenin in 7 steps from 17-deoxycortisone. The synthesis features a scalable enzymatic C14-H α-hydroxylation, a Bestmann ylide-enabled one-step construction of the butenolide motif, a late stage Mukaiyama hydration, and a stereoselective C11 carbonyl reduction.

Keywords
C–H hydroxylation; Mukaiyama hydration; cardiac glycosides; chemoenzymatic synthesis; protecting-group-free synthesis.
Products