title: Ligand-controlled regiodivergent pathways of rhodium(III)-catalyzed dihydroisoquinolone synthesis: experimental and computational studies of different cyclopentadienyl ligands.
abstract: Rh(III) -catalyzed directed C-H functionalizations of arylhydroxamates have become a valuable synthetic tool. To date, the regioselectivity of the insertion of the unsaturated acceptor into the common cyclometalated intermediate was dependent solely on intrinsic substrate control. Herein, we report two different catalytic systems that allow the selective formation of regioisomeric 3-aryl dihydroisoquinolones and previously inaccessible 4-aryl dihydroisoquinolones under full catalyst control. The differences in the catalysts are computationally examined using density functional theory and transition state theory of different possible pathways to elucidate key contributing factors leading to the regioisomeric products. The stabilities of the initially formed rhodium complex styrene adducts, as well as activation barrier differences for the migratory insertion, were identified as key contributing factors for the regiodivergent pathways.
authors.affiliation: Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne (Switzerland).
authors.forename: Matthew D
authors.initials: MD
authors.lastname: Wodrich
authors.forename: Baihua
authors.initials: B
authors.lastname: Ye
authors.forename: Jérôme F
authors.initials: JF
authors.lastname: Gonthier
authors.forename: Clémence
authors.initials: C
authors.lastname: Corminboeuf
authors.forename: Nicolai
authors.initials: N
authors.lastname: Cramer
keywords: density functional calculations; homogeneous catalysis; ligand control; rhodium; transition state theory