Centre for Catalysis Research & Innovation, Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
J Org Chem. 2010 Feb 19;75(4):1047-60. doi: 10.1021/jo902515z.
Through the introduction of an aryl chloride substituent, the selectivity of palladium-catalyzed direct arylation may be diverted to provide alternative regioisomeric products in high yields. In cases where low reactivity is typically observed, the presence of the carbon-chlorine bond can serve to enhance reactivity and provide superior outcomes. From a strategic perspective, the C-Cl bond is easily introduced and can be employed in a variety of subsequent transformations to provide a wealth of highly functionalized heterocycles with minimal substrate preactivation. The impact of the C-Cl functional group on direct arylation reactivity has also been evaluated mechanistically, and the observed reactivity profiles correlate very well with that predicted by a concerted metalation-deprotonation pathway.
通过引入芳基氯取代基，可以改变钯催化的直接芳基化反应的选择性，以高产率提供替代的区域异构体产物。在通常观察到低反应性的情况下，碳-氯键的存在可以增强反应性并提供更好的结果。从策略的角度来看，C-Cl 键易于引入，并可用于多种后续转化，以最小的底物预激活提供丰富的高度官能化杂环化合物。C-Cl 官能团对直接芳基化反应性的影响也从机理上进行了评估，观察到的反应性谱与协同金属化-脱质子化途径预测的反应性谱非常吻合。
