New Development of Electron Transfer in Co-ordination Compounds

本课题组拓展了过渡金属配位化合物和有机化合物与金属或低价金属盐结合的电子转移过程的研究。这些研究在有机电化学、电生化、有机化学、生物化学和有机合成等领域具有重要意义。在本次“有机电化学优先领域科学研究”期间，课题组的研究人员取得了以下成果：电子转移过程及其生成反应物质的研究：有机电化学中一种元素过程中金属到有机化合物的电子转移。发展了两个与金属到有机卤化物的受控电子转移有关的反应。一种是立体控制反应，在手性醛存在的情况下，由1,1-二卤代烷对映选择性生成手性结构块。这种新工艺将提供新的不对称合成方法。第二种是由另一种金属介导或催化的金属向二卤化物的选择性电子转移。二碘甲烷与纯锌反应得到收率高的碘甲基碘化锌；未检测到双金属物质双（碘）甲烷的形成。与纯锌反应相比，含催化量铅的锌处理二碘甲烷只产生二（碘）甲烷。用含铅锌或纯锌与PbCl_2的混合物处理碘甲基碘化锌生成二碘化甲烷，表明电子向碘甲基碘化锌的转移受铅催化剂的控制。新的电子转移体系的构建：为了开发高选择性反应，人们对新的电子转移体系进行了广泛的研究，这些反应是利用有机基团从配位化合物到底物的选择性电子转移和非对映选择性转移所产生的反应物质进行的。使用改性维生素B_<12>.3获得了一些成功的结果。生物化学相互作用中的电子传递过程：电化学发光探测生物活性得到了广泛的研究。利用该方法对dna界面抗肿瘤和抗病毒药物进行了表征。应用该方法对抗体识别进行了研究。少

Investigators of this group extended the research on electron transfer processes in transition metal coordination compounds and combination of organic compounds and metal or low-valent metal salts. These research are fundamentally important in organic electrochemistry, electrobiochemistry, organic chemistry, biochemistry, and organic synthesis. In the period of this Scientific Research on Priority Areas of Organic Electrochemistry, the investigators of the group produced the followihg results.1.Studies on Electron Transfer Process and Use of Generated Reactive Species : Electron transfer from metal to organic compounds in an elemental process in organic electrochemistry. Two reactions related to controlled electron transfer from metal to organic halides have been developed. One is stereocontrolled reaction containing enantioselective generation of chiral building block from 1,1-dihaloalkanes in the presence of chiral aldehydes. This novel process would provide new asymmetric synthesis … More of various organic compounds. Second one is selective electron transfer to dihalides from metal mediated or catalyzed by another metal. Diiodomethane reacted with pure zinc to give iodomethylzinc iodide in excellent yield ; formation of dimetallic species, bis (iodozincio) methane, could not be detected. In contrast to the reaction using pure zinc, treatment of diiodomethane with zinc containing catalytic amount of lead afforded bis (iodozincio) methane exclusively. Formation of bis (iodozincio) methane from iodomethylzinc iodide by treatment with zinc containing lead or a mixture of pure zinc and catalytic amount of PbCl_2 suggested that electron transfer to iodomethylzinc iodide was controlled by lead catalyst.2.Construction of New Electron Transfer System : New electron transfer systems have been extensively studies in order to develop highly selective reactions using reactive species generated by selective electron transfer and diastereoselective transfer of organic moieties from coordination compounds to substrates. Some successful results were obtained using modified Vitamin B_<12>.3.Electron Transfer Process in Biochemical Interaction : Electrochemical luminescence probing of biological activities have been extensively studied. DNA-interfacing antitumor and antiviral agents were characterized by using this process. Antibody recognition was also studied by applying the method. Less