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One‐Step Multigram‐Scale Biomimetic Synthesis of Psiguadial B
Author(s) -
Newton Christopher G.,
Tran Duc N.,
Wodrich Matthew D.,
Cramer Nicolai
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.201708333
Subject(s) - stereocenter , chemistry , natural product , cascade reaction , michael reaction , quinone methide , stereochemistry , cascade , cationic polymerization , benzaldehyde , intramolecular force , biosynthesis , combinatorial chemistry , enzyme , enantioselective synthesis , quinone , catalysis , organic chemistry , chromatography
A gram‐scale synthesis of psiguadial B, a purported inhibitor of human hepatoma cell growth, has been achieved in one step by a biomimetic three‐component coupling of caryophyllene, benzaldehyde, and diformylphloroglucinol. This cascade reaction is catalyzed by N,N′‐dimethylethylenediamine, and proceeds at ambient temperature to generate four stereocenters, two rings, one C−O bond, and three C−C bonds. Combined computational and experimental investigations suggest the biosynthesis of the natural product is non‐enzyme mediated, and is the result of a Michael addition between caryophyllene and a reactive ortho‐quinone methide, followed by two sequential intramolecular cationic cyclization events.