Schober João V, Laconsay Croix J, Wu Judy I
Department of Chemistry, University of Houston Houston TX 77204 USA
Chem Sci. 2024 Oct 8;15(43):18093-8. doi: 10.1039/d4sc05337k.
Computed gas-phase reaction profiles for Diels-Alder reactions, nucleus-independent chemical shifts, and bonding analyses for substituted and metal complexed, η-, η-, η-coordinated arenes reveal that dearomatization is necessary for arenes to exhibit ene- and diene-like reactivity. Substituted arenes and η-arenes exhibit high free energy barriers towards cycloaddition reactions, but strongly dearomatized η- and η-arenes can display low free energy barriers (∼20 kcal mol or less) for [4 + 2] cycloaddition reactions.
狄尔斯-阿尔德反应的计算气相反应剖面图、非核独立化学位移以及取代和金属络合的η-、η-、η-配位芳烃的键合分析表明，芳烃要表现出烯类和二烯类反应活性，去芳构化是必要的。取代芳烃和η-芳烃对环加成反应表现出较高的自由能垒，但高度去芳构化的η-和η-芳烃对[4 + 2]环加成反应可显示出较低的自由能垒（约20千卡/摩尔或更低）。
