Premium
Critical Switching of Cyclization Modes of Polyepoxides in Acidic Aqueous Media and Neutral Water: Synthesis and Revised Structure of a Nerolidol‐Type Sesquiterpenoid
Author(s) -
Nishikawa Keisuke,
Morita Kengo,
Hashimoto Subaru,
Hoshino Akihiro,
Ikeuchi Takumi,
Kumagai Momochika,
Morimoto Yoshiki
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201906039
Subject(s) - tetrahydropyran , chemistry , nerolidol , epoxide , cascade , aqueous solution , tetrahydrofuran , stereocenter , aqueous medium , stereochemistry , enantioselective synthesis , organic chemistry , solvent , ring (chemistry) , catalysis , chromatography , linalool , essential oil
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 H 2 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.