Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 136, Issue 15, Pages 5783-5789Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja5015508
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Funding
- NSF under the CCl Center for Selective C-H Functionalization [CHE-1205646]
- NSF [CHE-0749506]
- Center for High Performance Computing at the University of Utah
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1110599, 1205646] Funding Source: National Science Foundation
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Predicting site selectivity in C-H bond oxidation reactions involving heteroatom transfer is challenged by the small energetic differences between disparate bond types and the subtle interplay of steric and electronic effects that influence reactivity. Herein, the factors governing selective Rh-2(esp)(2)-catalyzed C-H amination of isoamylbenzene derivatives are investigated, where modification to both the nitrogen source, a sulfamate ester, and substrate are shown to impact isomeric product ratios. Linear regression mathematical modeling is used to define a relationship that equates both IR stretching parameters and Hammett sigma(+) values to the differential free energy of benzylic versus tertiary C-H amination. This model has informed the development of a novel sulfamate ester, which affords the highest benzylic-to-tertiary site selectivity (9.5:1) observed for this system.
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