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首页> 外文期刊>Chemistry: A European journal >An Experimental and Theoretical Study of the Mechanism of Stannylcupration of alpha,beta-Acetylenic Ketones and Esters
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An Experimental and Theoretical Study of the Mechanism of Stannylcupration of alpha,beta-Acetylenic Ketones and Esters

机译：α，β-乙炔酮和酯锡烷基化的机理的实验和理论研究

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摘要

The title reaction has been investigated by experimental and computational(DFT)techniques,and subsequently compared to the corresponding carbocupration reaction,with particular emphasis on the stereoselectiv-ity.For Stannylcupration of an ynone substrate,only the anti-addition product is observed,whereas for the corresponding ynoate substrate,the stereo-selectivity can be affected by the reaction conditions:in the presence of methanol as proton donor,the initial syn-addition product can be trapped,whereas a synlanti mixture is obtained in a non-protic solvent.This is in sharp contrast to the carbocupration of the same ynone substrate with a cyanocup-rate(RCu(CN)Li),which is highly selective for syn-addition.The product selectivities can be understood from a detailed computational characterization of the reaction paths,and in particular from the relative stabilities of the vinyl cuprate and allenolate intermediates.It is suggested that the ste-reodetermining step is protonation of vinyl cuprate intermediates.
机译：标题反应已通过实验和计算（DFT）技术进行了研究，随后与相应的碳cup合反应进行了比较，特别强调了立体选择性。对于炔酮基的甲磺酰胺化，仅观察到抗加成产物，而对于相应的叶酸酯底物，立体选择性会受到反应条件的影响：在甲醇作为质子供体的存在下，可以捕获初始的顺式加成产物，从而在非质子溶剂中获得顺式混合物。这与具有氰基合速率（RCu（CN）Li）的同一个炔酮底物的羰基化形成鲜明对比，后者对合成加成反应具有很高的选择性。可以通过详细的反应路径计算表征来了解产物的选择性。尤其是从铜酸乙烯酯和烯丙酸酯中间体的相对稳定性来看。铜酸盐中间体。

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