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A Carbene Catalysis Strategy for the Synthesis of Protoilludane Natural Products
Author(s) -
Hovey M. Todd,
Cohen Daniel T.,
Walden Daniel M.,
Cheong Paul H.Y.,
Scheidt Karl A.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201705308
Subject(s) - enantioselective synthesis , natural product , chemistry , carbene , combinatorial chemistry , catalysis , organocatalysis , stereochemistry , organic chemistry
The Armillaria and Lactarius genera of fungi produce the antimicrobial and cytotoxic mellolide, protoilludane, and marasmane sesquiterpenoids. We report a unified synthetic strategy to access the protoilludane, mellolide, and marasmane families of natural products. The key features of these syntheses are 1) the organocatalytic, enantioselective construction of key chiral intermediates from a simple achiral precursor, 2) the utility of a key 1,2‐cyclobutanediol intermediate to serve as a precursor to each natural product class, and 3) a direct chemical conversion of a protoilludane to a marasmane through serendipitous ring contraction, which provides experimental support for their proposed biosynthetic relationships.