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在[Cu~(2+)(OH~-)TMEDA]_2Cl_@~-催化下(TMEDA为N,N,N′,N′-四甲基乙二胺),α-氰基-p-X苯基乙酸乙酯(X=OCH_3,CH_3,Gl,H和NO_2)经氧化偶联反应,获得高产率的二聚体。产物中meso异构体的含量均大于dl异构体的含量。IR,~1HNMR和EPR对反应过程研究结果表明,反应机理为底物以CN取代催化剂中的OH~-,生成反应中间体配合物,OH~-夺取底物的α-H,产生相应的碳负离子,碳负离子向Cu~(2+)单电子转移生成自由基,自由基偶合而生成产物。氧将Gu~+氧化为Cu~(2+),使反应继续进行。
Under the catalysis of [Cu ~ (2 +) (OH ~ -) TMEDA] _2Cl_ ~ ~ (TMEDA is N, N, N ’, N’-tetramethylethylenediamine) Ethyl acetate (X = OCH_3, CH_3, Gl, H and NO_2) was oxidatively coupled to obtain a high yield of dimer. The content of the meso isomers in the product is greater than the content of the dl isomer. The results of IR, ~ 1HNMR and EPR showed that the reaction mechanism was as follows: the reaction mechanism was replaced by CN with OH ~ - in the catalyst to form the intermediate of the reaction and OH ~ - to seize the α-H of the substrate to produce the corresponding carbon Negative ions, carbanions to Cu ~ (2+) single electron transfer to generate free radicals, free radical coupling to produce the product. Oxygen oxidizes Gu ~ + to Cu ~ (2+) and the reaction proceeds.