Abstract

A comparative study was made of the differential selectivity of the Sonogashira reaction with a pair of competing arylacetylenes under “ligand- and copper-free” conditions by varying nature and concentration of aryl halides and bases common to competing substrates. The change in the differential selectivity with varying nature of aryl halides is consistent with the proposal that aryl halide and arylacetylene are activated sequentially according to a mechanism that is linear in terms of chemical kinetics. The observed lack of influence of the nature and concentration of the base on the selectivity of the reaction under competition between arylacetylenes indicates that the step of their activation is virtually irreversible.

中文翻译：

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Sonogashira 反应“无配体和铜”条件下底物激活的线性和非线性（协同）机制的区别

摘要

通过改变芳基卤化物和竞争底物共有的碱基的性质和浓度，对在“无配体和无铜”条件下与一对竞争性芳基乙炔进行的 Sonogashira 反应的差异选择性进行了比较研究。不同选择性随芳基卤化物性质的变化而变化，这与芳基卤化物和芳基乙炔根据化学动力学线性机制依次活化的提议一致。观察到碱的性质和浓度对芳乙炔之间竞争下反应的选择性没有影响，这表明它们的活化步骤实际上是不可逆的。