Full mechanistic evaluation of new reactions requires significant time and resources. One potential way of reducing the chemical footprint of mechanistic discovery is through the development of autonomous reaction finding (ARF) through quantum chemistry. Recently, our group reported the development of a program designed for rapid quantum mechanical investigation of reaction pathways. We then set out to test this program via a tandem experimental and computational investigation of Csp3-N, Csp3-F, and Csp3- Csp2 reductive elimination from model palladium (IV) complexes. Through analysis of more than 1500 transition states we evaluated the relevant portions of the potential energy surface of this system. Using these data we successfully predicted the most effective substrates for Csp3-N reductive elimination. Experimental kinetics data indicated that the predicted ΔGǂ were in close correlation with experimentally measured values. Furthermore, we were able to use the initial reaction information generated by the ARF program to put forth a plausible mechanism for the remaining Csp3-F and Csp3- Csp2 reductive elimination process and predict qualitatively correct product distributions for various substrates. The predicted products and ratios were confirmed experimentally demonstrating the plausibility of computationally driven development of new main group and group 10 reactions.

Experimental and computational investigation of Csp3-N, Csp3-F, and Csp3- Csp2 reductive elimination from model palladium (IV) complexes

249th National Meeting (2015)

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