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Synthesis of Illisimonin a Skeleton by Intramolecular Diels–Alder Reaction of Ortho-Benzoquinones and Biomimetic Skeletal Rearrangement of Allo-Cedranes

Takahiro Suzuki, Riko Nagahama, Muhammad Aiman Fariz, Yuki Yukutake, Kazutada Ikeuchi, Keiji Tanino

Organics · pp. 306–312 · Published 2 Sep 2021

10.3390/org2030016

Abstract

Illisimonin A is a new sesquiterpene isolated from Illicium simonsii, and it possesses a novel 5/5/5/5/5 pentacyclic skeleton. The tricyclic skeleton of illisimonin A, tricyclo[5.2.1.01,5]decane, is presumed to be biosynthesized from allo-cedranes via a skeletal rearrangement. Herein, we report the concise synthesis of highly oxidized allo-cedranes by an intramolecular Diels–Alder reaction using ortho-benzoquinones and demonstrate the biomimetic transformation of allo-cedranes by a retro-Claisen/aldol pathway.

Intramolecular force Chemistry Sesquiterpene Aldol reaction Diels–Alder reaction Claisen rearrangement Skeleton (computer programming) Stereochemistry

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