Shilpi Kumari
Chemistry
September 2021
In CÀH activation chemistry, distantly directed clusters of bifunctional molecules do not necessarily behave independently of each other. A superior Ir catalyst for the chemoselective CÀH deuteration of bifunctional arylsulfonamides is presented by combined DFT and exploratory mechanistic studies. This is a concrete and useful example of how to forecast intramolecular directing group chemo selectivity using constraining energies in a pharmaceutical context. The major catalysis of sulfonamide-selective CÀH deuteration has been mediated by careful catalyst design driven solely by subjective substrate catalytic limiting free energy predictions. This enabled intramolecular discrimination between competing ortho-directed assemblies in CÀH activation. In this way, the required chemoselective restriction of the sulfonamide moiety was achieved, giving the inherently more surprising pyrazole-directed ensemble present in the linked molecule. A meticulous investigation of his DFT calculations and mechanisms uncovered the breakdown of the applied constrained free energy model, providing control over ligand design, substrate mathematics and collection cooperativity in supporting DFT calculations. , and significant interdependence of solvation was shown. This research has significant ramifications for endeavors to forecast intramolecular C-H activation directing gathering chemo selectivity utilizing improved monofunctional component molecules.
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© Airo Journals 2021
