Endo-oxacyclizations of polyepoxides: Biomimetic synthesis of fused polycyclic ethers

Frank E. McDonald, Fernando Bravo, Xia Wang, Xudong Wei, Motoki Toganoh, J. Ramón Rodríguez, Bao Do, Wade A. Neiwert, Kenneth I. Hardcastle

研究成果: ジャーナルへの寄稿学術誌査読

82 被引用数 (Scopus)

抄録

Boron trifluoride-etherate promotes the endo-selective oxacyclization of polyepoxides derived from various acyclic terpenoid polyalkenes, including geraniol, farnesol, and geranylgeraniol, providing an efficient and stereoselective synthesis of substituted oxepanes and fused polyoxepanes. The mechanism of the oxacyclization reaction probably involves intramolecular nucleophilic addition of epoxide oxygen to open another epoxide that is activated as an electrophile by the Lewis acid. These oxacyclizations proceed stereospecifically with inversion of configuration upon opening of each epoxide to provide trans-fused polycyclic products. The oxacyclization cascade is terminated by a tethered nucleophile, which may be the carbonyl oxygen of a ketone, ester, or carbonate, or a trisubstituted alkene. The best oxacyclization yields are generally observed with tert-butyl carbonate as the terminating nucleophile, although in some cases the oxacyclization products include formation of tert-butyl ethers as a minor product. The oxacyclization transformations described herein may mimic ring-forming steps in the biosynthesis of trans-syn-trans-fused polycyclic ether marine natural products.

本文言語英語
ページ(範囲)2515-2523
ページ数9
ジャーナルJournal of Organic Chemistry
67
8
DOI
出版ステータス出版済み - 4月 19 2002
外部発表はい

!!!All Science Journal Classification (ASJC) codes

  • 有機化学

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