Structural Revision and Biomimetic Synthesis of Goupiolone B. (18th August 2017)

• Record Type: Journal Article
• Authors: Matsuo, Yosuke; Yoshida, Ayane; Saito, Yoshinori; Tanaka, Takashi
• Is Part Of: Angewandte Chemie. Volume 129:Number 39(2017)
• Page Start: 12017
• Page End: 12021
• Publication Date: 2017-08-18
• Subjects: Biomimetische Synthesen -- Naturstoffe -- Oxidationen -- Strukturaufklärung -- Umlagerungen; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201706532
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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.