| Project/Area Number |
62550636
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | KINKI UNIVERSITY |
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Principal Investigator |
KIKUKAWA Kiyoshi Kinki University, 九州工学部, 教授 (60037918)
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| Project Period (FY) |
1987 – 1988
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| Project Status |
Completed (Fiscal Year 1988)
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| Budget Amount *help |
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1988: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1987: ¥1,500,000 (Direct Cost: ¥1,500,000)
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| Keywords | Regioselectivity / Stereospecificity / Hydrometallation / Aryldemetallation / Complex Catalyst / Alkenylsilanes / Alkenylgermanes / アリール化脱メタル反応 / ヒドロスタニル化 / アルケニルスズ化合物 / トランスメタレーション / 芳香族ジアゾニウム塩 / 立体選択的オレフィン合成 / アルケニルケイ素化合物 / 非対称ジアリールテルル |
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| Research Abstract |
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.
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