Synthesis of heterocyclic analogues of epibatidine via 7-azabicyclo[2.2.1]hept-2-yl radical intermediates. 1. Intermolecular reactions.
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).
Gómez-Sánchez
Elena
E
Laboratorio de Radicales Libres, IQOG (CSIC), C/Juan de la Cierva 3, 28006-Madrid, Spain.
Soriano
Elena
E
Marco-Contelles
José
J
D000181:Acrylonitrile / Q000737:chemistry; D053961:Azabicyclo Compounds / Q000737:chemistry*; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis*; D003486:Cyanides / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry*; D006536:Heptanes / Q000737:chemistry*; D008956:Models, Chemical; D018722:Nicotinic Agonists / Q000138:chemical synthesis*; D011725:Pyridines; D011978:Receptors, Nicotinic / Q000378:metabolism*; D013237:Stereoisomerism
D053961:Azabicyclo Compounds; D019086:Bridged Bicyclo Compounds, Heterocyclic; D003486:Cyanides; D005609:Free Radicals; D006536:Heptanes; D018722:Nicotinic Agonists; D011725:Pyridines; D011978:Receptors, Nicotinic; C082748:epibatidine; D000181:Acrylonitrile