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Reaction Pathways and Redox States in α‐Selective Cobalt‐Catalyzed Hydroborations of Alkynes

Clemens K. Blasius, Vladislav Vasilenko, Regina Matveeva, Hubert Wadepohl, Lutz H. Gade

2020Angewandte Chemie International Edition54 citationsDOIOpen Access PDF

Abstract

Cobalt(II) alkyl complexes supported by a monoanionic NNN pincer ligand are pre-catalysts for the regioselective hydroboration of terminal alkynes, yielding the Markovnikov products with α:β-(E) ratios of up to 97:3. A cobalt(II) hydride and a cobalt(II) vinyl complex appear to determine the main reaction pathway. In a background reaction the highly reactive hydrido species specifically converts to a coordinatively unsaturated cobalt(I) complex which was found to re-enter the main catalytic cycle.

Topics & Concepts

CobaltCatalysisHydroborationChemistryRegioselectivityCatalytic cycleMarkovnikov's ruleLigand (biochemistry)Pincer movementMedicinal chemistryRedoxAlkylHydridePolymer chemistryOrganic chemistryMetalReceptorBiochemistryOrganoboron and organosilicon chemistryCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling Reactions
Reaction Pathways and Redox States in α‐Selective Cobalt‐Catalyzed Hydroborations of Alkynes | Litcius