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Divergent Biomimetic Total Syntheses of Ganocins A–C, Ganocochlearins C and D, and Cochlearol T
Author(s) -
Shao Hui,
Gao Xiaonan,
Wang ZhongTian,
Gao Ziwei,
Zhao YuMing
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202000677
Subject(s) - intramolecular force , chemistry , aromatization , regioselectivity , stereochemistry , phenol , nucleophile , combinatorial chemistry , organic chemistry , catalysis
A divergent synthetic approach to six Ganoderma meroterpenoids, namely ganocins A–C, ganocochlearins C and D, and cochlearol T, has been developed for the first time. This synthetic route features a two‐phase strategy which includes early‐stage rapid construction of a common planar tricyclic intermediate followed by highly selective late‐stage transformations into various Ganoderma meroterpenoids. Key to the strategy are a bioinspired intramolecular hetero‐Diels–Alder reaction and Stahl‐type oxidative aromatization, allowing efficient formation of the common tricyclic phenol intermediate. A nucleophilic dearomatization of the phenol unit, combined with a regioselective 1,4‐reduction of the resulting dienone, enabled rapid access to ganocins B and C. Additionally, site‐selective Mukaiyama hydration, followed by an intramolecular oxa ‐Michael addition/triflation cascade, served as a key strategic element in the chemical synthesis of ganocin A.