By using an iterative ligand design approach, we were able to combine the respective strengths of computational chemistry and experimental kinetic measurements for the CuH-catalyzed hydroamination of unactivated terminal olefins to identify more reactive ligands. Using DFT calculations and ligand-substrate interaction model, utilizing energy decomposition analysis (ALMO-EDA 2), we identified the combination of several factors that play an important role in the design of a more active ligand: attractive, noncovalent ligand–substrate interactions, electronic effects and ligand stability in order to systematically modify ligand structure. This led to the development of more effective ligands, thus avoiding synthesizing and testing a large library of ligands. Using a mechanically guided ligand design approach, a new ligand (SEGFAST) for the CuH-catalyzed hydroamination reaction of unactivated terminal olefins has been developed, providing a 62-fold rate increase over reactions compared to DTBM-SEGPHOS, the previous optimal ligand.

Computationally study of ligand effects using ligand substrate interaction model: Design of ligands that significantly improve the efficiency of CuH-catalyzed hydroamination reactions

2019 Fall National Meeting

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