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Structural Revision and Biomimetic Synthesis of Goupiolone B
Author(s) -
Matsuo Yosuke,
Yoshida Ayane,
Saito Yoshinori,
Tanaka Takashi
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201706532
Subject(s) - racemization , chemistry , catechol , nonane , stereochemistry , biomimetic synthesis , oxidative coupling of methane , enantioselective synthesis , computational chemistry , organic chemistry , catalysis
Goupiolones A and B are unique phenolic compounds with significant DNA‐damaging activity. In this study, the structure of goupiolone B was revised on the basis of DFT calculations of the 13 C NMR chemical shifts and biosynthetic considerations. The dibenzobicyclo[3.2.2]nonane skeleton of the revised structure suggested that goupiolone B was produced by oxidative coupling between catechol and goupiolone A, which was strongly supported by biomimetic synthesis. Furthermore, racemization of goupiolone B was observed during the attempted resolution of its racemic mixture. A plausible racemization mechanism involving α‐ketol rearrangement is proposed.