23396-36-3Relevant articles and documents
Asymmetric Synthesis of 2,3-Disubstituted Cyclic Ketones by Enantioselective Conjugate Radical Additions
Nad, Sukanya,Sibi, Mukund P.
, (2019)
Enantioselective conjugate radical addition to 2-acyloxymethyl cycloalkenones proceeds in high yield with outstanding diastereoselectivity and excellent enantioselectivity using chiral salen Lewis acids. The process provides access to 2,3-disubstituted cycloalkanones, a structural motif present in natural products.
Deciphering Reactivity and Selectivity Patterns in Aliphatic C-H Bond Oxygenation of Cyclopentane and Cyclohexane Derivatives
Martin, Teo,Galeotti, Marco,Salamone, Michela,Liu, Fengjiao,Yu, Yanmin,Duan, Meng,Houk,Bietti, Massimo
supporting information, p. 9925 - 9937 (2021/06/30)
A kinetic, product, and computational study on the reactions of the cumyloxyl radical with monosubstituted cyclopentanes and cyclohexanes has been carried out. HAT rates, site-selectivities for C-H bond oxidation, and DFT computations provide quantitative information and theoretical models to explain the observed patterns. Cyclopentanes functionalize predominantly at C-1, and tertiary C-H bond activation barriers decrease on going from methyl- and tert-butylcyclopentane to phenylcyclopentane, in line with the computed C-H BDEs. With cyclohexanes, the relative importance of HAT from C-1 decreases on going from methyl- and phenylcyclohexane to ethyl-, isopropyl-, and tert-butylcyclohexane. Deactivation is also observed at C-2 with site-selectivity that progressively shifts to C-3 and C-4 with increasing substituent steric bulk. The site-selectivities observed in the corresponding oxidations promoted by ethyl(trifluoromethyl)dioxirane support this mechanistic picture. Comparison of these results with those obtained previously for C-H bond azidation and functionalizations promoted by the PINO radical of phenyl and tert-butylcyclohexane, together with new calculations, provides a mechanistic framework for understanding C-H bond functionalization of cycloalkanes. The nature of the HAT reagent, C-H bond strengths, and torsional effects are important determinants of site-selectivity, with the latter effects that play a major role in the reactions of oxygen-centered HAT reagents with monosubstituted cyclohexanes.
Stereochemical Insights into the Anaerobic Degradation of 4-Isopropylbenzoyl-CoA in the Denitrifying Bacterium Strain pCyN1
Küppers, Julian,Becker, Patrick,Jarling, René,D?rries, Marvin,Caki?, Nevenka,Schmidtmann, Marc,Christoffers, Jens,Rabus, Ralf,Wilkes, Heinz
supporting information, p. 4722 - 4731 (2019/03/13)
The constitutions and absolute configurations of two previously unknown intermediates, (1S,2S,4S)-2-hydroxy-4-isopropylcyclohexane-1-carboxylate and (S)-3-isopropylpimelate, of anaerobic degradation of p-cymene in the bacterium Aromatoleum aromaticum pCyN
