Rh-Catalyzed Cascade C–C/C<sub>olefin</sub>–H Activations and Mechanistic Insight
Yuxi Wang, Bo Qiu, Lingfei Hu, Gang Lü, Tao Xu
Abstract
A reverse concerted metalation–deprotonation (CMD) process has been proposed as a key step to rationalize our newly discovered Rh-catalyzed C–C/Colefin–H cascade reaction to access 1-benzazepines. The reaction features redox-neutral conditions with 100% atom economy and showed broad substrate scope and good efficiency (23 examples, up to 85% yield). DFT calculations indicated that the reverse CMD process is a key step to kinetically override the normal “cut and sew” process and rendered the sequential olefinic C–H activation/reductive elimination as the predominant pathway.
Topics & Concepts
ChemistryYield (engineering)CatalysisDeprotonationOlefin fiberSubstrate (aquarium)MetalationStereochemistryReductive eliminationCascadeCascade reactionCombinatorial chemistryComputational chemistryOrganic chemistryMaterials scienceOceanographyGeologyMetallurgyIonChromatographyCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling ReactionsCyclopropane Reaction Mechanisms