Analyzing Site Selectivity in Rh2(esp)2-Catalyzed Intermolecular C–H Amination Reactions
Citations Over TimeTop 10% of 2014 papers
Abstract
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.
Related Papers
- → Efficient synthesis of highly substituted pyrroles based on the tandem reactions: intermolecular amination and Pd(II)-catalyzed intramolecular hydroamidation(2008)32 cited
- → On the nature of the electronic effect of multiple hydroxyl groups in the 6-membered ring – the effects are additive but steric hindrance plays a role too(2017)16 cited
- → Electronic and steric effects of substituents in 1,3-diphenylprop-2-yn-1-one during its reaction with Ru3(CO)12(2018)10 cited
- → Electronic and steric effects in the control of the Anilinium chloride catalyzed condensation reaction between Aldones and 4-Phenylthiosemicarbazide(2013)4 cited
- → ChemInform Abstract: PdII‐Catalyzed Intermolecular Amination of Unactivated C(sp3)—H Bonds.(2016)