权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Development of Bio-mimic Electrochemical Reaction by using Cobalt Complex and Its Application

钴配合物仿生电化学反应的研究进展及其应用

基本信息

批准号：
16550104
负责人：
KAWAFUCHI Hiroyuki
金额：
$ 1.92万
依托单位：
Toyama National College of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

We developed a tin-free method for carbon radical generation by using cobaloxime, which was used as a mimic of metalloenzyme vitamine B_<12>. Regeneration of low valency cobalt catalyst was carried out by electroreduction with a sacrifical Zn anode in an undivided cell system. Development of a catalytic radical generation method is very meaningful in the synthesis of commonly useful compounds.1.We investigated the 1,2-acyl rearrangement of 2-(halomethyl)cyclopentane-1,3-diones, giving the corresponding cyclohexane-l,4- diones by the electrochemical radical generation method. This reaction was utilized for the synthesis of functionalized biaryls. The electroreduction of monoacetals of 2-(halomethyl)cyclopentane-1,3-diones in the presence of cobaloxime as a catalyst afforded the cyclohexane-1,4-dione monoacetals in good yields. The Bu_3SnH-reduction of 2-aryl-2-(halomethyl)cyclopentane- 1,3-diones under refluxing in benzene resulted in the rearrangement, affording the corresponding cyclohexane-1,4-diones, and 1,4- hydroquinones proceeded in moderate yields when heating was prolonged.2.We present here the radical cyclization reaction of O-alkyloximes by using cobalt complex-sacrificial electrode system, giving functionalized β-aminoacetals. The radicals generated from primary, secondary, and tertialy alkyl bromides added to the carbon- nitrogen double bonds without any difficulty and difference in their reactivity. This reaction seems to be slightly influenced by steric factor in the cyclization process.3.We investigated the three component combination reaction of bromoacetal with benzaldehyde, giving the corresponding cyclization product by the electrochemical radical generation method. The best result was obtained by using [Co^<III>(N_4)Cl_2]ClO_4 as a cobalt complex.

我们开发了一种利用钴肟作为金属酶模拟物的无锡生成碳自由基的方法。在连续槽系统中，采用牺牲锌阳极电还原的方法对低价钴催化剂进行了再生。1.研究了2-(卤甲基)环戊烷-1，3-二酮的1，2-酰基重排反应，用电化学自由基发生方法得到了相应的环己烷-L，4-二酮。利用该反应合成了功能化联芳基化合物。2-(卤甲基)环戊烷-1，3-二酮在钴肟催化下电还原得到高产率的环己烷-1，4-二酮单缩醛。在苯中回流，2-芳基-2-(卤甲基)环戊烷-1，3-二酮在Bu_3SnH-还原反应中发生重排反应，生成相应的环己烷-1，4-二酮，延长加热时间，1，4-对苯二酚以中等的产率进行。2.采用钴配合物-牺牲电极体系对O-烷基肟类化合物进行自由基环化反应，得到功能化的β-氨基缩醛。伯烷基溴、仲烷基溴和叔烷基溴生成的自由基加到碳-氮双键上，反应活性没有任何困难和差异。该反应在环化过程中受空间位阻因素的影响较小。3.研究了溴缩醛与苯甲醛的三组分组合反应，用电化学自由基生成法给出了相应的环化产物。以[Co^&lt；III&gt；(N_4)Cl_2]ClO_4为钴络合物时效果最好。