Hydroamination of unactivated olefins is a highly desirable synthetic method for the construction of amine-containing organic compounds. Our group has reported phosphine-p-arene rhodium catalysts for this transformation and studied the mechanism through experimental physical organic methods, but improved catalysts have been difficult to discover. In order to better understand the features of the catalytic reaction, the mechanism for intramolecular hydroamination of aminoalkenes by rhodium catalysts was investigated computationally. Nine stationary points on and off the catalytic cycle were selected for further investigation. The influence of the ligand on these ground- and transition-state geometries was investigated by varying ligand scaffold structure. In addition, the influence of electron-donating and electron-withdrawing groups on the bound arene and phosphine were examined.

Design of new rhodium hydroamination catalysts through in silico ligand screening

248th National Meeting (2014)

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