Critical Switching of Cyclization Modes of Polyepoxides in Acidic Aqueous Media and Neutral Water: Synthesis and Revised Structure of a Nerolidol‐Type Sesquiterpenoid. Issue 30 (3rd July 2019)

• Record Type: Journal Article
• Authors: Nishikawa, Keisuke; Morita, Kengo; Hashimoto, Subaru; Hoshino, Akihiro; Ikeuchi, Takumi; Kumagai, Momochika; Morimoto, Yoshiki
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 30(2019)
• Page Start: 10168
• Page End: 10172
• Publication Date: 2019-07-03
• Subjects: biomimetic synthesis -- cyclization -- diastereoselectivity -- natural products -- terpenoids; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201906039
• Languages: English
• ISSNs: 1433-7851

Abstract

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. Abstract : The epoxide‐opening cascade cyclization of polyepoxides affords tetrahydrofuran (THF) products in acidic aqueous media and 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.