A <i>meta</i>‐Selective C−H Alumination of Mono‐Substituted Benzene by Using An Alkyl‐Substituted Al Anion through Hydride‐Eliminating S<sub>N</sub>Ar Reaction
Satoshi Kurumada, Kengo Sugita, Ryo Nakano, Makoto Yamashita
Abstract
Abstract Reaction of an Al‐centered anion with toluene proceeded to form C−H cleaved product with a perfect meta‐selectivity and a relatively small kinetic isotope effect (KIE, k H /k D =1.51). DFT calculations suggested a two‐step reaction mechanism and electronically controlled meta‐selectivity arising from the electron‐donating methyl group. The reaction with other mono‐substituted arenes was also investigated.
Topics & Concepts
TolueneSelectivityChemistryKinetic isotope effectHydrideBenzeneAlkylIonMedicinal chemistryReaction mechanismPhotochemistryOrganic chemistryHydrogenDeuteriumCatalysisQuantum mechanicsPhysicsCoordination Chemistry and OrganometallicsOrganoboron and organosilicon chemistryCatalytic C–H Functionalization Methods