Acid-Promoted Rearrangement of Cyclic α,β-Epoxy Acylates:  Stereoselective Synthesis of Spirocyclanes and Quaternary Carbon Centers

Yasuyuki Kita,* Shinji Kitagaki, Yutaka Yoshida, Sachiko Mihara, Dai-Fei Fang, Michinori Kondo, Sachi Okamoto, Reiko Imai, Shuji Akai, and Hiromichi Fujioka
Faculty of Pharmaceutical Sciences, Osaka University, 1-6, Yamada-oka, Suita, Osaka, 565, Japan
J. Org. Chem., 1997, 62 (15), pp 4991–4997
DOI: 10.1021/jo970035q
Publication Date (Web): July 25, 1997
Copyright © 1997 American Chemical Society
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

Abstract

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The rearrangement reaction of α,β-epoxy acylates in cyclic systems was studied. The treatment of cis-derivatives with a Lewis acid afforded rearranged products via the regioselective β-cleavage of the oxirane ring due to the electron-withdrawing nature of the acyloxy group, whereas trans-derivatives enhanced the neighboring group participation to yield only a small amount of rearranged products. This rearrangement reaction proved to be useful for the construction of a variety of spirocyclane systems or quaternary carbon centers on rings and could be applied to their syntheses as optically active forms.

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History

  • Published In Issue July 25, 1997
  • Received January 3, 1997

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