Mechanistically Guided Workflow for Relating Complex Reactive Site Topologies to Catalyst Performance in C–H Functionalization Reactions

Autor:	Ryan C. Cammarota, Wenbin Liu, John Bacsa, Huw M. L. Davies, Matthew S. Sigman
Rok vydání:	2022
Předmět:	Kinetics Colloid and Surface Chemistry Coordination Complexes Thermodynamics Rhodium Stereoisomerism General Chemistry Methane Biochemistry Carbon Catalysis Hydrogen
Zdroj:	Journal of the American Chemical Society. 144:1881-1898
ISSN:	1520-5126 0002-7863
DOI:	10.1021/jacs.1c12198
Popis:	Leveraging congested catalyst scaffolds has emerged as a key strategy for altering innate substrate site-selectivity profiles in C-H functionalization reactions. Similar to enzyme active sites, optimal small molecule catalysts often feature reactive cavities tailored for controlling substrate approach trajectories. However, relating three-dimensional catalyst shape to reaction output remains a formidable challenge, in part due to the lack of molecular features capable of succinctly describing complex reactive site topologies in terms of numerical inputs for machine learning applications. Herein, we present a new set of descriptors, "Spatial Molding for Approachable Rigid Targets" (SMART), which we have applied to quantify reactive site spatial constraints for an expansive library of dirhodium catalysts and to predict site-selectivity for C-H functionalization of 1-bromo-4-pentylbenzene via donor/acceptor carbene intermediates. Optimal site-selectivity for the terminal methylene position was obtained with Rh
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::50f031ea51d3aaec28a99cd032f9ca1b https://doi.org/10.1021/jacs.1c12198 Zobrazit plný text záznamu