A combined experimental and computational study reveals a crossover between conventional cross-coupling and carbene insertion pathways in a Pd catalyzed C(sp 2 )–H insertion

作者：Arushi Tyagi, Kritika Gaur, Anubhav Goswami, Arko Seal, Mayuk Joddar, Garima Jindal · 发表于：Chemical Science · 年份：2025 · DOI：10.1039/d5sc00777a · 被引用次数：4 · 研究领域：Cyclopropane Reaction Mechanisms、Catalytic C–H Functionalization Methods、Catalytic Cross-Coupling Reactions

). Our VTNA study reveals the order to be one in both diazo and indole, which along with microkinetic modelling aligns well with the computationally predicted mechanism. The mechanism is further supported by the detection of the most stable intermediate in the catalytic cycle using ESI-HRMS. An investigation into the origin of stereoselectivity using DLPNO-CCSD(T) presents a new paradigm, wherein stereocontrol arises during the formation of the Pd carbene itself as opposed to proton transfer steps found for all other metal catalysts.