Mechanistic insight into theOrganocalcium-mediatedNucleophilicAlkylation ofBenzene andFurtherRationalDesign

Xuefei Zhao, Dengmengfei Xiao, Xianlu Cui, Chaoqun Chai and Lili Zhao *

Institute of Advanced Synthesis, School of Chemistry and MolecularEngineering, Nanjing Tech University, Nanjing 211816, China.

Abstract：DFT calculations have been performed to study the recently reported unprecedented nucleophilicalkylation of benzene mediated by an organocalcium compound. The studyreveals that the dimeric reaction mechanism is kinetically more favorable, and the rate-determining step ispredicted to be the first nucleophilic attack of benzene by the organocalcium compound. Remarkably, thedimeric mechanism involves the formation of NMR detected dimeric alkyl calcium analogue4, whichagrees well with the experimental observations. EDA-NOCV analysis indicated that the origin of the higherreactivity of alkylcalcium1lies in its unusual bonding nature. We further studied the ligand effects andrationally designed the [(^SiMe3BDI)CaEt]₂molecule, which shows a higher reactivity towards benzene. Inaddition, wede novodesigned the more reactive heavier alkylstrontium and alkylbarium congeners, whichmight be targets for experimental synthesis.

本论文封面以太极图为灵感，单金属中心机理和双金属中心机理对立又统一地阐明了苯的亲核取代反应机理。

Catalysis Science & Technology, 2020, 10, 950–958（内封面文章，影响因子：5.726）

论文链接：https://pubs.rsc.org/en/content/articlelanding/2020/cy/c9cy02252j#!divAbstract