Synergetic Cp*Rh(III)/Zn2+-Prompted Arylamination of Alkylalkenes: Reaction Development and Mechanistic Insight

Arylethylamines are not only privileged intermediates in organic synthesis but also a type of core structural motif widely found in both pharmaceutical and material sciences. Therefore, there is an urgent need to develop practical and straightforward strategies toward their synthesis, among which the carboamination of ubiquitous alkenes should be one of the most ideal strategies, but it still represents great challenges, especially for alkylalkenes, due to their relatively inert reactivity and elusive chemoselectivity control. We report herein a mild, redox-neutral, and chemo-/regioselective Cp*Rh(III)-catalyzed arylamination of diverse unactivated alkylalkenes by judicious choice of N-phenoxy amides as both the C- and N-sources and ZnCl₂ as the master additive, whereby two classical and alternative β-H elimination pathways are completely suppressed; instead, the carboamination scenario is delivered in a controllable and highly selective manner. Through a combined computational and experimental mechanistic study, the unique synergetic catalytic mode mediated by the additive effect is reasonably clarified, thereby providing a solid reference for modern synergistic catalytic C–H functionalization chemistry.