Synthesis 2018; 50(21): 4263-4269
DOI: 10.1055/s-0036-1589138
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© Georg Thieme Verlag Stuttgart · New York

Acetic Anhydride Mediated Retro-Ene Reaction via a [4.4.3]Propel­lane Skeleton Intermediate Containing a Quaternary Ammonium Linkage

Noriki Kutsumura
a   International Institute for Integrative Sleep Medicine (WPI-IIIS), University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8575, Japan
,
Takahiro Okada
b   Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki-305-8571, Japan   Email: nagase.hiroshi.gt@u.tsukuba.ac.jp
,
Satomi Imaide
c   Laboratory of Medicinal Chemistry, School of Pharmacy, Kitasato University, 5-9-1 Shirokane, Minato-ku, Tokyo 108-8641, Japan
,
Hideaki Fujii
c   Laboratory of Medicinal Chemistry, School of Pharmacy, Kitasato University, 5-9-1 Shirokane, Minato-ku, Tokyo 108-8641, Japan
,
Hiroshi Nagase*
a   International Institute for Integrative Sleep Medicine (WPI-IIIS), University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8575, Japan
b   Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki-305-8571, Japan   Email: nagase.hiroshi.gt@u.tsukuba.ac.jp
› Author Affiliations
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Publication History

Received: 19 October 2017

Accepted: 26 October 2017

Publication Date:
13 December 2017 (online)


Published as part of the Special Section on the 26th French–Japanese Symposium on Medical and Fine Chemistry

Abstract

A novel retro-ene reaction via a [4.4.3]propellane intermediate containing a quaternary ammonium linkage was developed. The feature of this acetic anhydride mediated rearrangement includes the elimination of an acetoxy group at the C14 position and subsequent intramolecular nucleophilic addition of a nitrogen functional group to form an isolable ammonium salt intermediate. We clarified the reaction mechanism utilizing the deuterated derivative.

Supporting Information