Biomimetic Synthesis of the CDE Ring Moiety of Physalins, Complex 13,14-Secosteroids

Yusuke Araki; Atsuo Nakazaki; Toshio Nishikawa

doi:10.1021/acs.orglett.0c04198

Biomimetic Synthesis of the CDE Ring Moiety of Physalins, Complex 13,14-Secosteroids

Org Lett. 2021 Feb 5;23(3):989-994. doi: 10.1021/acs.orglett.0c04198. Epub 2021 Jan 14.

Authors

Yusuke Araki¹, Atsuo Nakazaki¹, Toshio Nishikawa¹

Affiliation

¹ Graduate School of Bioagricultural Sciences, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8601, Japan.

PMID: 33444499
DOI: 10.1021/acs.orglett.0c04198

Abstract

Physalins are a structurally complex family of 13,14-secosteroids isolated from the genus Physalis. We disclose a two-step construction of the CDE ring moiety of the physalins from a steroidal compound bearing 14-OH, 18-COOMe, and 17, 20-α-epoxide based on our biosynthetic proposal. C13-C14 bond cleavage by an alkoxy radical at C-14 and spontaneous epoxide ring opening gave a compound having a cyclononene and γ-lactone. Diastereoselective dihydroxylation of the resulting alkene with OsO₄ provided the CDE ring moiety of physalin.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Biomimetics
Molecular Structure
Physalis / chemistry*
Physalis / metabolism
Secosteroids / chemical synthesis
Secosteroids / chemistry*
Steroids / chemical synthesis
Steroids / chemistry*

Substances

Secosteroids
Steroids