Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
J Am Chem Soc. 2010 Mar 3;132(8):2496-7. doi: 10.1021/ja9077528.
The reversal of regioselectivity in a Pd-catalyzed cross-coupling reaction of an aryl chloro triflate with different ligands, established by Fu and co-workers, has been studied computationally. C-O insertion was found to be controlled by Pd-HOMO ArO-LUMO interaction, where C-Cl insertion is facilitated by the lower C-Cl TS distortion energy. The greater reactivities of monoligated Pd species are due primarily to the lack of distortion of the Pd species.
由 Fu 及其同事建立的芳基氯三氟甲磺酸酯与不同配体的 Pd 催化交叉偶联反应中区域选择性的反转已通过计算进行了研究。C-O 插入被认为由 Pd-HOMO ArO-LUMO 相互作用控制，而 C-Cl 插入则由较低的 C-Cl TS 变形能促进。单配位 Pd 物种的更高反应性主要归因于 Pd 物种的变形缺乏。
