Electroreductive intramolecular cyclisation of bromoalkoxylated derivatives catalysed by nickel(I) tetramethylcyclam in "green" media

被引：19

作者：

Medeiros, M. J. ^{[1
]}

Neves, C. S. S. ^{[1
]}

Pereira, A. R. ^{[1
]}

Dunach, E. ^{[2
]}

机构：

[1] Univ Minho, Ctr Quim, P-4704553 Braga, Portugal

[2] Univ Nice Sophia Antipolis, CNRS, UMR 6001, Chim Bioorgan Lab, F-06108 Nice 2, France

来源：

ELECTROCHIMICA ACTA | 2011年 / 56卷 / 12期

关键词：

Microemulsions; Electrosynthesis; Catalytic reduction; Intramolecular cyclisation; Nickel(II) complex; CARBON BOND FORMATION; RADICAL CYCLIZATION; ALKYL-HALIDES; MICROEMULSION STRUCTURE; ELECTROCHEMICAL REDUCTION; TETRAAZA MACROCYCLE; COMPLEXES; DIMETHYLFORMAMIDE; CATHODES; BROMIDES;

D O I：

10.1016/j.electacta.2011.02.054

中图分类号：

O646 [电化学、电解、磁化学];

学科分类号：

081704 ;

摘要：

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. (c) 2011 Elsevier Ltd. All rights reserved.

引用

页码：4498 / 4503

页数：6

共 44 条

[1] KINETICS AND MECHANISM OF THE ALKYLNICKEL FORMATION IN ONE-ELECTRON REDUCTIONS OF ALKYL-HALIDES AND HYDROPEROXIDES BY A MACROCYCLIC NICKEL(I) COMPLEX [J].