Publicação

Electroreductive intramolecular cyclization of bromoalkoxylated derivatives catalyzed by nickel(I) tetramethylcyclam in "green" media

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Detalhes bibliográficos
Resumo:The (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetra-decane)nickel(I), [Ni(tmc)]+, electrogenerated at glassy carbon cathodes is shown to be an effective catalyst for the intramolecular radical-type cyclisation of bromoalkoxylated derivatives 1 in alcohol and / or alcohol/water mixtures as well as in microemulsions made with cationic and anionic surfactants. The results obtained indicate that the reaction proceeds via cleavage of the carbon–bromine bond to form a radicaltype intermediate that undergoes cyclisation on the unsaturated C-C bond to afford substituted tetrahydrofurans. The reactions are more selective and take place at higher current density than when carried out in conventional aprotic solvents.
Autores principais:Medeiros, M. J.
Outros Autores:Neves, C. S. S.; Pereira, A. R.; Duñach, E.
Assunto:Microemulsions Electrosynthesis Catalytic reduction Intramolecular cyclisation Nickel(II) complex
Ano:2011
País:Portugal
Tipo de documento:artigo
Tipo de acesso:acesso aberto
Instituição associada:Universidade do Minho
Idioma:inglês
Origem:RepositóriUM - Universidade do Minho
Descrição
Resumo:The (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetra-decane)nickel(I), [Ni(tmc)]+, electrogenerated at glassy carbon cathodes is shown to be an effective catalyst for the intramolecular radical-type cyclisation of bromoalkoxylated derivatives 1 in alcohol and / or alcohol/water mixtures as well as in microemulsions made with cationic and anionic surfactants. The results obtained indicate that the reaction proceeds via cleavage of the carbon–bromine bond to form a radicaltype intermediate that undergoes cyclisation on the unsaturated C-C bond to afford substituted tetrahydrofurans. The reactions are more selective and take place at higher current density than when carried out in conventional aprotic solvents.