Biomimetic Total Syntheses of (+)-Chloropupukeananin, (-)-Chloropupukeanolide D, and Chloropestolides

Takahiro Suzuki; Soichiro Watanabe; Wataru Ikeda; Susumu Kobayashi; Keiji Tanino

doi:10.1021/acs.joc.1c02108

Biomimetic Total Syntheses of (+)-Chloropupukeananin, (-)-Chloropupukeanolide D, and Chloropestolides

J Org Chem. 2021 Nov 5;86(21):15597-15605. doi: 10.1021/acs.joc.1c02108. Epub 2021 Oct 21.

Authors

Takahiro Suzuki¹, Soichiro Watanabe², Wataru Ikeda², Susumu Kobayashi³, Keiji Tanino¹

Affiliations

¹ Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Hokkaido, Japan.
² Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810, Hokkaido, Japan.
³ Faculty of Pharmaceutical Sciences, Tokyo University of Science, 2641 Yamazaki, Noda 278-8510, Chiba, Japan.

PMID: 34672579
DOI: 10.1021/acs.joc.1c02108

Abstract

Chloropupukeananin, chloropupukeanolides, and chloropestolides are a family of structurally complex bioactive natural products that possess highly functionalized tricyclo[4.3.1.0^3,7]decane or bicyclo[2.2.2]octane skeletons. Biosynthesis of the chloropupukeananin family is triggered by the intermolecular heterodimeric Diels-Alder reaction between maldoxin and iso-A82775C; however, the enzymes involved have not yet been identified. We herein report the one-pot biomimetic synthesis of chloropupukeananin and chloropupukeanolide D. Moreover, the effect of the solvent on the intermolecular Diels-Alder reaction of siccayne and maldoxin suggested that the biosynthesis of the chloropupukeananin family involves a Diels-Alderase-catalyzed heterodimeric Diels-Alder reaction.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Biomimetics*
Cycloaddition Reaction
Sesquiterpenes*

Substances

Sesquiterpenes
chloropupukeananin
chloropupukeanolide D