Synthesis of Heterocyclic Analogues of Epibatidine via 7-Azabicyclo[2.2.1]hept-2-yl Radical Intermediates. 1. Intermolecular Reactions

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• 作者：Elena Gó ; mez-Sá ; nchez ; Elena Soriano ; José ; Marco-Contelles
• 刊名：Journal of Organic Chemistry
• 出版年：2008
• 出版时间：September 5, 2008
• 年：2008
• 卷：73
• 期：17
• 页码：6784-6792
• 全文大小：367K
• 年卷期：v.73,no.17(September 5, 2008)
• ISSN：1520-6904

文摘

The synthesis and reactivity of the 7-azabicyclo[2.2.1]hept-2-yl radical has been extensively investigated in inter- and intramolecular reaction processes for the first time. In this work we will present the preparation of the radical and its successful intermolecular reaction with radical acceptors such as tert-butylisocyanide and acrylonitrile. Computational analyses have been carried out to show and explain the mechanisms and stereochemical outcome of these transformations. Overall and from the chemical point of view, a new and convenient synthetic approach has been developed for the synthesis of exo-2-(cyano)alkyl substituted 7-azabicyclo[2.2.1]heptane derivatives, a series of compounds of wide interest for the synthesis of heterocyclic analogues of epibatidine. As a result, we describe here the synthesis of the tetrazoloepibatidines (8 and 15) and the oxadiazoloepibatidine (10).