Senior Investigators: Prof. John Hartwig (UI-UC), Prof. Karen Goldberg (U. Wash.).

The discovery of efficient catalysts for the hydroamination of alkenes could have a tremendous impact on the synthesis of pharmaceuticals, of fine chemicals and of commodity chemicals. Especially desirable would be a process that allows the selective formation of the anti-Markovnikov product (Scheme 1). The Hartwig and Goldberg laboratories are collaborating to find solutions to this challenging and as yet unsolved synthetic problem.

In order to achieve the anti-Markovnikov hydroamination of alkenes, complexes of late transition metals are being studied as potential catalysts reacting by the mechanism shown in Scheme 2. While steps A and B are well documented for a variety of metals, examples of the formation of alkyl C-N bonds by reaction between a transition metal alkyl complex and an amine (step C) are rare. Therefore, a major focus of the research has been to further our knowledge and understanding of this step. The discovery of such an elementary reaction could be used to create additional valuable chemical processes.

Scheme 2. General catalytic cycle for the title reaction. Highlighted in red is the alkyl C-N bond formation step.