Unified Total Synthesis of 3-epi-Ryanodol, Cinnzeylanol, Cinncassiols A and B, and Structural Revision of Natural Ryanodol and Cinnacasol

Angewandte Chemie
Masaki KoshimizuMasayuki Inoue

Abstract

Ryanodane diterpenoids structurally share an extremely complex fused ring system, but differ in the substitution patterns of the hydroxy groups. Since these congeners exhibit various biologically important functions, their efficient chemical constructions have been greatly anticipated. We previously accomplished the total synthesis of ryanodine (1) using pentacycle 8 as the advanced intermediate. Here, we report the unified total syntheses of four distinct diterpenoids, 3-epi-ryanodol (3), cinnzeylanol (4), cinncassiols B (5), and A (6), from 8, all within 10 steps. A series of highly optimized chemo- and stereoselective reactions and protecting-group manipulations enabled assembly of the densely oxygenated structures of 3-6. Furthermore, the present synthetic studies established the C13S stereochemisty of 5-7 and revised the proposed structures of natural ryanodol (2) and cinnacasol (7) to be those of 3 and 6, respectively.

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Citations

Aug 27, 2016·Science·Kangway V ChuangSarah E Reisman
Feb 6, 2017·Chemistry : a European Journal·Yi-An GuoTao Ye
Sep 7, 2017·Natural Product Reports·James R Hanson
Mar 25, 2016·Chemical & Pharmaceutical Bulletin·Kengo MasudaMasayuki Inoue
Sep 22, 2020·Chemistry : a European Journal·Huilin LiXuegong She
Feb 9, 2021·The Journal of Organic Chemistry·Stefanie MayrHendrik Zipse
Feb 24, 2021·Accounts of Chemical Research·Sara E DibrellSarah E Reisman
Mar 9, 2021·Journal of Natural Products·Suk Woo ChangDae Sik Jang
Mar 9, 2018·Chemical Reviews·Lei LiYanxing Jia
Oct 26, 2021·Chemistry : a European Journal·Stefanie Mayr, Hendrik Zipse

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