Addition of 1,3-dicarbonyl compounds to the cycloheptatriene derivatives

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2009
Südemen, M. Burak
The one electron oxidant Mn(OAc)3 has been used for years for the oxidative addition of 1,3-dicarbonyls to alkenes to give dihydrofuranes. Since cycloheptatriene is in equilibrium with its valance isomer norcaradiene, it will be interesting to study the reaction of CHT derivatives with Mn(OAc)3 in the presence of 1,3-dicarbonyls. In our research, we have observed that unsubstituted cycloheptatriene gave CHT based products. However, when electron withdrawing -CN group was attached to C-7 position of CHT we obtained norcaradiene based products. We have also observed that there exist an equilibrium between [3+2] addition products through 1,5-hydride shift. In addition, we obtained dihydrofurane derivatives in the presence of Mn(OAc)3 from compounds which have already formed C-C bond between 1,3- dicarbonyl and alkene. Formation of dihydrofurane derivatives from these compounds brought up two questions; whether cyclization is going over oxygen atom or not and whether reaction involves a cyclopropane intermediate or not. Despite all efforts, we could not manage to synthesize the required material for the investigation of these questions.

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Citation Formats
M. B. Südemen, “Addition of 1,3-dicarbonyl compounds to the cycloheptatriene derivatives,” M.S. - Master of Science, Middle East Technical University, 2009.