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Synfacts 2008(4): 0356-0356  
DOI: 10.1055/s-2008-1042863
Synthesis of Heterocycles
© Georg Thieme Verlag Stuttgart · New York

W(CO)5-Catalyzed Synthesis of 2- and 3-Azabicyclo[3.3.0]octanes

Contributor(s): Victor Snieckus, Wei Gan
Y. Onizawa, H. Kusama, N. Iwasawa*
Tokyo Institute of Technology, Japan
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Publication History

Publication Date:
19 March 2008 (online)

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Significance

Reported is a tungsten-catalyzed regioselective synthesis of 3-azobicyclo[3.3.0]-octane and 2-azobicyclo[3.3.0]octane derivatives C and D from π-acetylenic dienol silyl ether 1. The reaction proceeds via different pathways a and b as a function of base. Thus, the initial vinylidene complex A undergoes double cyclizations and nitrogen facilitated 1,2-alkyl migration to lead to product C. This mechanism is substantiated by 13C- as indicated and D-labeled experiments. In the absence of base, the tungsten-catalyzed process is envisaged to proceed via the zwitterionic intermediates B to lead to products D. None of the intermediates were isolated.