Analyzing site selectivity in Rh2(esp)2-catalyzed intermolecular C-H amination reactions.
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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 Rh2(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 σ(+) 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.
Published Version (Please cite this version)10.1021/ja5015508
Publication InfoBess, EN; DeLuca, RJ; Du Bois, J; Oderinde, MS; Roizen, Jennifer Lyn; Sigman, Matthew S; & Tindall, DJ (2014). Analyzing site selectivity in Rh2(esp)2-catalyzed intermolecular C-H amination reactions. J Am Chem Soc, 136(15). pp. 5783-5789. 10.1021/ja5015508. Retrieved from http://hdl.handle.net/10161/13797.
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Assistant Professor of Chemistry
Inspired by small molecule natural products, the Roizen laboratories will initiate research to access improved antibiotics, and selective ion channel inhibitors, with implications for the study and treatment of cancer, heart disease, and neurological disorders. This program will begin with the development of novel reaction methods, and where appropriate these methodologies will be advanced through mechanistic investigations. New reactions will be designed to streamline access to challenging nat