Enantioselective Ruthenium-Catalyzed C–H Alkylations by a Chiral Carboxylic Acid with Attractive Dispersive Interactions
Uttam Dhawa, Robert Connon, João C. A. Oliveira, Ralf Steinbock, Lutz Ackermann
Abstract
Asymmetric ruthenium-catalyzed C–H alkylations were enabled by a chiral C2-symmetric carboxylic acid. The mild cooperative ruthenium(II) catalysis set the stage for the assembly of chiral tetrahydrocarbazoles and cyclohepta[b]indoles with high levels of enantioselectivity at room temperature. Mechanistic studies by experiment and computation identified a fast C–H ruthenation, along with a rate- and enantio-determining proto-demetalation. The asymmetric induction was governed by weak attractive secondary dispersion interactions as found in NCI analysis of the key transition states.
Topics & Concepts
RutheniumEnantioselective synthesisChemistryCatalysisCombinatorial chemistryDispersion (optics)Asymmetric inductionStereochemistryOrganic chemistryPhysicsOpticsCatalytic C–H Functionalization MethodsAsymmetric Hydrogenation and CatalysisSynthesis and Catalytic Reactions