Crossed McMurry Coupling Reactions for Porphycenic Macrocycles: Non-Statistical Selectivity and Rationalisation.
Crossed McMurry Coupling Reactions for Porphycenic Macrocycles: Non-Statistical Selectivity and Rationalisation.
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DOI：
10.1002/ejoc.201500221
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发表时间：
2015-06
影响因子：
2.8
通讯作者：
Bebbington MW
中科院分区：
文献类型：
--
作者：
Cowie TY;Kennedy L;Żurek JM;Paterson MJ;Bebbington MW
首次研究了联苯并联苯甲醛与联吡咯二醛的交叉McMurry反应。只有那些源自同源偶联McMurry产品的成斑大环才被形成。用密度泛函理论和电子传播子计算对双醛起始物质的电子亲和力进行了模拟，并对结果进行了解释。首次合成了一种新型的二氧杂二硫杂茂环烯，证实了这一点，并预测了二苯并呋喃和联噻吩环的交叉偶联。这种方法将允许事先确定相关交叉麦克默里反应的可行底物。
Crossed McMurry reactions of bifuran- or bithiophenedicarbaldehydes with bipyrroledicarbaldehydes have been studied for the first time. Only those porphycenic macrocycles derived from homocoupled McMurry products were formed. The results are explained by using both density functional theory and electron propagator computations to model the electron affinity of the dialdehyde starting materials. It was predicted that bifuran\bithiophene cross-coupling would indeed occur, and this was demonstrated by the first synthesis of a novel dioxa,dithio hetero-porphycenoid annulene. This approach will allow the prior identification of viable substrates for related crossed McMurry reactions.