Critical Switching of Cyclization Modes of Polyepoxides in Acidic Aqueous Media and Neutral Water: Synthesis and Revised Structure of a Nerolidol-Type Sesquiterpenoid

Keisuke Nishikawa; Kengo Morita; Subaru Hashimoto; Akihiro Hoshino; Takumi Ikeuchi; Momochika Kumagai; Yoshiki Morimoto

doi:10.1002/anie.201906039

Critical Switching of Cyclization Modes of Polyepoxides in Acidic Aqueous Media and Neutral Water: Synthesis and Revised Structure of a Nerolidol-Type Sesquiterpenoid

Angew Chem Int Ed Engl. 2019 Jul 22;58(30):10168-10172. doi: 10.1002/anie.201906039. Epub 2019 Jul 3.

Authors

Keisuke Nishikawa¹, Kengo Morita¹, Subaru Hashimoto¹, Akihiro Hoshino¹, Takumi Ikeuchi¹, Momochika Kumagai^{1

2}, Yoshiki Morimoto¹

Affiliations

¹ Department of Chemistry, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka, 558-8585, Japan.
² Japan Food Research Laboratories, Ibaraki-shi, Osaka, 567-0085, Japan.

PMID: 31211481
DOI: 10.1002/anie.201906039

Abstract

Biomimetic epoxide-opening cascades of polyepoxides enable the efficient and rapid construction of polyether frameworks. Herein, we show that the epoxide-opening cascade cyclization that affords tetrahydrofuran products in acidic aqueous media produces tetrahydropyran (THP) in neutral water. THP formation proceeded by simply heating polyepoxides in neutral water and followed a different cyclization mode from those observed so far. The novel cascade cyclization in H₂ O was applied to the synthesis of a new nerolidol-type sesquiterpenoid, resulting in revision of the proposed structure and determination of the absolute configuration.

Keywords: biomimetic synthesis; cyclization; diastereoselectivity; natural products; terpenoids.

Publication types

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

Abstract

Publication types

Grants and funding