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Synthesis of Organometallic Compounds of Group IV, V, and V Typical Elements and Their Application for C-C Bond Formation

IV、V、V族典型元素有机金属化合物的合成及其在C-C键形成中的应用

基本信息

批准号：
62550636
负责人：
KIKUKAWA Kiyoshi
金额：
$ 1.28万
依托单位：
KINKI UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

项目摘要

1. Transition metal-catalyzed hydrometalation(Si,Ge,Sn) of terminal acetylenes. In the presence of RhCl(CO)(PPh_3)_2, PHC CD reacts with Bu_3SnH regio-and stereo-specifically to give (E)-Ph(Bu_3Sn)=CHD. The rhodium-catalyzed hydrogermination and hydrosilylation of RC CH also regiospecifically give R(R'_3M)C=CH_2(M=Ge,Si) in contrast to the platinum-catalyzed hydrosilylation. The most effective catalyst is Rh(acac)(CH_2=CH_2)_2.2. Palladium-catalyzed aryldemetallation of alkenylmetal compounds. Syn-addition of Ar-Pd to double bond and anti-elimination of Pd-SnR_3 play an important role in the palladium-catalyzed aryldestannylation of (E)-Ph(Bu_3Sn)C=CHD with ArN_2BF_4 giving (Z)-PhcH=CDAr Ar-Pd-X aryldestannylate PhcH=CHSnPh_3 by addition-elimination mechanism or transmetallation mechanism depending on the sub-stituents on the aryl group and the ligands of palladium. Facile aryldesilylation and aryldegerminylation were obaserved in the palladium-catalyzed reaction of ArN_2BF_4 with alkenylsilanes and alkenylgermanes, respectively. A reaction of RCH=CHMR'_3(M=Si, Ge) with Ar-Pd-OAc give arylated products, RCH=C(Ar)MR'_3.3. Synthesis of unsymmetrical diaryltellurium from Ar'N_2BF_4 and ArTeH. An addition of Ar'N_2BF_4 to a solution of ArTeH prepared from ArTeTeAr-NaBH_4 or ArTeMgBr-H_2O system yields unsymmetrical disryltellurium in moderate to good yields.

1. 过渡金属催化末端乙炔的氢金属化(Si,Ge,Sn)。在存在 RhCl(CO)(PPh_3)_2 的情况下，PHC CD 与 Bu_3SnH 区域特异性和立体特异性反应生成 (E)-Ph(Bu_3Sn)=CHD。与铂催化的氢化硅烷化反应相比，铑催化的氢萌发和RC CH 的氢化硅烷化反应也区域特异性地产生R(R'_3M)C=CH_2(M=Ge,Si)。最有效的催化剂是Rh(acac)(CH_2=CH_2)_2.2。钯催化烯基金属化合物的芳基脱金属。 Ar-Pd 与双键的顺加成和 Pd-SnR_3 的反消除在钯催化 (E)-Ph(Bu_3Sn)C=CHD 与 ArN_2BF_4 的芳基去甲锡烷基化反应中发挥重要作用，通过加成-消除机制或金属转移得到 (Z)-PhcH=CDAr Ar-Pd-X 芳基去甲锡烷基化物 PhcH=CHSnPh_3 机制取决于芳基上的取代基和钯的配体。在钯催化的 ArN_2BF_4 与烯基硅烷和烯基锗烷的反应中，分别观察到容易的芳基脱甲硅烷基化和芳基脱锗基化。 RCH=CHMR'_3(M=Si,Ge)与Ar-Pd-OAc的反应得到芳基化产物RCH=C(Ar)MR'_3.3。由Ar'N_2BF_4和ArTeH合成不对称二芳基碲。将Ar'N_2BF_4 添加到由ArTeTeAr-NaBH_4 或ArTeMgBr-H_2O 体系制备的ArTeH 溶液中，以中等至良好的产率产生不对称二甲基碲。