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Mechanism and Origins of Ligand-Controlled Linear Versus Branched Selectivity of Iridium-Catalyzed Hydroarylation of Alkenes

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journal contribution
posted on 04.02.2016, 15:22 by Genping Huang, Peng Liu
The iridium-catalyzed carbonyl-directed hydroarylation of monosubstituted alkenes developed by Bower and co-workers [Crisenza, G. E. M.; McCreanor, N. G.; Bower, J. F. J. Am. Chem. Soc. 2014, 136, 10258–10261] provides an efficient strategy for highly branched-selective hydroarylation of both aryl- and alkyl-substituted alkenes. Density functional theory calculations in the present study revealed that the unique regiochemical control in this reaction is due to an unconventional modified Chalk–Harrod-type mechanism. Instead of the commonly accepted Chalk–Harrod-type mechanism of transition metal-catalyzed hydroarylation that involves C–H oxidative addition, olefin migratory insertion into the Ir–H bond, and C–C reductive elimination, the Ir-catalyzed reaction occurs via migratory insertion of the olefin into the Ir–aryl bond and C–H reductive elimination. The experimentally observed ligand-controlled selectivity is attributed to a combination of electronic and steric effects in the selectivity-determining olefin migratory insertion step. Ligand steric contour maps show that, in reactions with large-bite-angle bisphosphine ligands, such as dFppb, the steric repulsions between the substrate and the aryl substituents on the ligand lead to complete branched selectivity, and the linear selectivity in reactions with small-bite-angle ligands is due to electronic effects that favor 2,1-olefin migratory insertions.