CROSS-COUPLING REACTIONS BETWEEN SP^2-CARBON AND SP CARBON USING PALLADIUM COMPLEXES AND COPPER IODIDE

使用钯配合物和碘化铜进行 SP^2-碳和 SP 碳之间的交叉偶联反应

• 批准号: 11640549
• 负责人: SONOGASHIRA Kenkichi
• 金额: $ 2.18万
• 依托单位: Fukui University 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640549/
• 关键词: Complex catalysts; Pd-Cu Catalysts; Cross-coupling; terminal acetylenes; SP^2 Carbon halides; SP^2-炭素ハライド

The Pd/Cu-catalyzed cross-coupling reaction between sp^2 C halides and terminal acetylenes provides a useful method for synthesizing conjugated alkynes that have found application in diverse area ranging from anticancer drugs to material science. The cross coupling reaction of terminal acetylenes with aromatic bromides using standard catalytic systems, (Ph_3P)_2PdCl_2/CuI/amine, requires higher temperature, which may cause some oligomerization of acetylenes, than those of the corresponding iodides. The following optimum catalytic conditions for the coupling of aryl bromides with phenyl acetylene are obtained ; phenyl acetylene (1.5 equiv.), C_6H_5Br(1.0 equiv.), Bu_4NI(10 mol%), CuI(4 mol%), DMF/^nBuNH_2=20/1 70℃. The catalyst, (PhCN)_2PdCl_2/^tBu_3P,/CuI containing electron rich bulky phosphine, have recently been shown to be effective for the cross-coupling of aryl bromides at room temperature [S. L. Buchwald. et al, Org. Lett.,2, 1729(2000)]. The Pd-complex catalyst containing electron rich bulky phosphine such as (R_3P)_2PdCl_2,R_3P = P^tBu_2, P^tBu_2(o-C_6H_4OMe), P^tBu_2Ph, P^tBu_2(C_4H_3S) and 1,1 bis(ditertiarybutyl)phosphinoferrocene, can be also used as an alternative to the above system. From the comparison of the catalytic activities of three types of mononuclear Pd complexes, L_2PdCl_2, dinuclear Pd complexes, (R_3P)_2Pd_2Cl_4, and Chelate Pd complexes, L-LPdCl_2, we conclude that the equilibrium, L_2Pd 【tautomer】 LPd + L, for the mononuclear Pd complexes, and an aqueous solvents for the chelate phosphine complex play a role in the catalytic cycle, respectively.

钯/铜催化的卤化物与末端乙炔之间的交叉偶联反应为合成共轭炔烃提供了一种有用的方法，在抗癌药物和材料科学等领域都有广泛的应用。在标准催化体系(Ph_3P)_2PdCl2/CuI/胺的催化下，末端乙炔与芳香溴化物的交叉偶联反应需要较高的温度，这可能导致乙炔的某些齐聚反应。得到了芳基溴化物与苯乙炔偶联反应的最佳催化条件：苯乙炔(1.5当量)、C_6H_5Br(1.0当量)、Bu4Ni(10mol%)、CuI(4mol%)、DMF/^nBuNH_2=20/170℃。(PHCN)_2PdCl2/Tbu_3P/CuI催化剂最近被证明对芳基溴化物在室温下的交叉偶联反应是有效的[S.L.Buchwald]。等人，Org.李特，2,1729(2000)]。含(R_3P)_2PdCl2、R_3P=P^Tbu_2、P^Tbu_2(o-C_6H_4OMe)、P^Tbu_2Ph、P^Tbu_2(C_4H_3S)和1，1-二(二叔丁基)膦二茂铁等Pd络合物催化剂也可作为上述体系的替代品。通过对L_2PdCl2、双核Pd络合物、(R_3P)_2Pd_2Cl4三种单核Pd络合物和L-LPdCl2三种单核Pd络合物催化活性的比较，得出单核Pd络合物的平衡L_2Pd[互变构体]LPd+L和螯合膦络合物的水溶剂分别在催化循环中起作用的结论。

项目成果

K.Sonogashira: "Palladium-Catalyzed Alkynylation-Sonogashira Alkyne Synthesis in Handbook of Organopalladium Chemistry for Organic Synthesis"John Wiley & Sons, New York. 493-530 (2002)

K.Sonogashira：“有机钯化学有机合成手册中的钯催化炔基化-Sonogashira 炔烃合成”John Wiley

Kenkichi Sonogashira: "Palladium-Catalyzed Alkynylation-Sonogashira Alkyne Synthesis"Handbook of Organopalladium Chemistry for Organic Synthesis. 493-530 (2002)

Kenkichi Sonogashira：《钯催化的炔基化-Sonogashira 炔烃合成》有机合成有机钯化学手册。

K, Sonogashira: "Development of Pd-Cu catalyzed cross-coupling of terminal acetylenes with sp^2-carbon halides"J. Organometal. Chem.. (2002)

K，Sonogashira：“Pd-Cu 催化末端乙炔与 sp^2-碳卤化物交叉偶联的发展”J。

K.Sonogashira: "Palladium-Catalyzed Alkynylation-Sonogashira Alkeyne Synthesis in Handbook of Organopalladium Chemistry for Organic Synthesis"John Wiley & Sons, New York. 493-530(38) (2002)

K.Sonogashira：“有机钯化学有机合成手册中的钯催化炔基化-Sonogashira 炔烃合成”John Wiley

Kenkichi Sonogashira: "Development of Pd-Cu catalyzed cross-coupling of terminal acetylenes with sp^2-carbon halides"J. Organometal. Chem.. (2002)

Kenkichi Sonogashira：“Pd-Cu催化末端乙炔与sp^2-碳卤化物交叉偶联的发展”J。