Studies on Structure and Reactivity of Novel Organometallic Reagents

该研究组的研究人员扩展了新功能化有机金属试剂的生成和使用试剂的新合成方法的创新研究。研究的重点是多功能有机金属试剂的产生，主要是双金属试剂，以及利用多金属络合物体系开发新的高选择性反应。本课题取得的主要研究成果如下：1.偕二金属试剂的制备及合成应用研究提出了利用铅催化的偕二卤化物与锌反应直接制备偕二锌试剂的可能性。然后，以良好的产率获得了gem-双锌试剂。所得到的双金属试剂RCH（ZnX）_2（其中R=H、Me、Me_3Si等）在有机合成、羰基化合物（包括酯）的烯化反应、亲电试剂的分步反应等方面有着重要的应用。 ...更多信息 发现了一种非手性二卤代物的α-卤代烷基结构单元：SmI_2介导的1，1-二碘乙烷与手性醛反应，高非对映选择性地生成手性卤代醇。生成手性1-碘乙基反应性嵌段。2-溴乙酸乙酯在低温下选择性地生成4-二碘硫杂-3-氧代丁酸乙酯，后者与酮和混合酸酐反应分别生成羟基酮酯和二酮酯。3.有机硅功能化试剂的有机合成。4.锰在有机合成中的应用研究了有机锰和锰配合物的一些有机反应，报道了利用这些锰物种对不饱和键的立体选择性加成和有机卤化物的还原进行有机合成。少

Investigators of this group extended the research on generation of new functionalized organometallic reagents and innovation on new synthetic methodologies using the reagents. Research was focused on the generation of multifunctional organometallic reagents, mainly dimetallic reagents, and the development of new highly selective reactions using multi-metal complex system. Main research results obtained within the term of the research project are follows.1.Studies on gem-Dimetallic Reagents : Generation and Synthetic Applications.A possibility of direct preparation of gem-dizinc reagents from gem-dihalides was suggested by the use of Pb-catalyzed reaction with Zn. Then, gem-dizinc reagents have been obtained in good yields. Dimetallic reagents thus obtained, RCH (ZnX)_2 where R=H,Me, Me_3Si etc, are useful in organic synthesis ; olefination of carbonyl compounds including ester, and stepwise reaction of electrophiles.2.New Reactions using Organolanthanoid Reagents.Generation of chiral a … More lpha-haloalkyl building block from achiral dihalides has been discovered : SmI_2-mediated reaction of 1,1-diiodoethane with chiral aldehydes gave chiral halohydrin in high diastereoselective manner. Chiral 1-iodoethyl reactive block was generated. Ethyl 2-bromoacetate gives ethyl 4-diiodosamario-3-oxo-butanoate selectively in low temperature, whose reaction with ketones and mixed anhydrides afforded hydroxy keto esters and diketo esters, respectively.3.Organic Synthesis Using Functional Organosilicon Reagents.Several synthetic reactions using silacyclobutane, dibromomethylsilanes, and acylsilanes have been disclosed. Various new carbon-carbon forming reactions have been studied, including threecomponent coupling of haloacylsilanes, acylsilane, and carbonyl compounds.4.Use of Manganese in Organic Synthesis.Some organic reactions using organomanganese and manganese ate-complexes have been studied ; organic synthesis using these manganese species in stereoselective addition to unsaturated bonds and reduction of organic halides were reported. Less