Directed Cobalt-Catalyzed <i>anti</i>-Markovnikov Hydroalkylation of Unactivated Alkenes Enabled by “Co–H” Catalysis
Dandan Yang, Hai Huang, Menghui Li, Xiao‐Ju Si, He Zhang, Jun‐Long Niu, Mao‐Ping Song
Abstract
The earth-abundant cobalt-catalyzed anti-Markovnikov hydroalkylation of unactivated alkenes with oxime esters was achieved by introducing an 8-aminoquinoline directing group on the alkenes. The catalytic system, consisting of commercially available Co(acac)3 and PhMeSiH2, enables the construction of unfunctionalized C(sp3)–C(sp3) bonds and features exclusive anti-Markovnikov selectivity, good functional group tolerance, and the avoidance of an extra ligand, oxidant, or base. Mechanistic insight into this new catalytic system indicates the involvement of both alkyl radical and cobalt hydride intermediates.
Topics & Concepts
Markovnikov's ruleChemistryCatalysisCobaltCombinatorial chemistryLigand (biochemistry)AlkylOrganic chemistryAlkeneFunctional groupMedicinal chemistryRegioselectivityPolymerReceptorBiochemistryCatalytic C–H Functionalization MethodsRadical Photochemical ReactionsSulfur-Based Synthesis Techniques