Intramolecular and Intermolecular Mn(III)-Induced Carbon Monoxide Trapping Reactions of Alkynes with Malonate and Cyano Ester Units
Intramolecular and Intermolecular Mn(III)-Induced Carbon Monoxide Trapping Reactions of Alkynes with Malonate and Cyano Ester Units
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Mn(III) 诱导的炔烃与丙二酸酯和氰基酯单元的分子内和分子间一氧化碳捕获反应
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发表时间：
1996
期刊：
影响因子：
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通讯作者：
H. Alper
中科院分区：
文献类型：
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作者：
Kazumi Okuro;H. Alper
利用Mn(III)诱导的氧化体系研究了炔与丙二酸酯和氰酸酯的分子内和分子间一氧化碳捕获反应。苯乙炔在乙酸乙酯−CH3CN(1：1)中与丙二酸二乙酯反应，得到(Z)-4，4-二甲氧基-2-苯基-2-己烯酸。同样，4-炔基丙二酸酯和氰基乙酸酯的分子内反应在相同的条件下进行区域和立体选择性反应，以适中的产率得到相应的亚甲基环烷基羧酸。该反应涉及一氧化碳捕获乙烯基自由基，这些自由基是由锰(III)诱导的丙二酸根或氰乙酸根加成到炔烃中而形成的。
Intra- and intermolecular carbon monoxide trapping reactions of alkynes with malonates and cyano esters were developed using a Mn(III)-induced oxidative system. Phenylacetylene was treated with diethyl ethylmalonate in the presence of Mn(OAc)3·2H2O, in AcOH−CH3CN (1:1) under carbon monoxide, affording (Z)-4,4-dicarbethoxy-2-phenyl-2-hexenoic acid. Similarly, intramolecular reactions of 4-alkynylmalonates and cyanoacetates proceeded regio- and stereoselectively under the same conditions to afford the corresponding methylenecycloalkanecarboxylic acids in moderate yields. The reaction involves carbon monoxide trapping of vinyl radicals which are formed by the addition of malonate or cyanoacetate radicals induced by Mn(III) to alkynes.