Functionalization of saturated hydrocarbons

N-Heterocycles as ligands in complex catalysts for selective functionalization of saturated hydrocarbons 92ACR504. 

The selective functionalization of saturated hydrocarbons. Part 44. Measurement of size of reagent by variation of steric demands of competing substrates using Gif chemistry. Tetrahedron, 54, 3379-3390 (b) Chen, K., Costas, M., Kim, J., Tipton, A. K. and Que,... 

The fundamental problem in the functionalization of saturated hydrocarbons is that their components, carbon and hydrogen, do not have lone electron pairs, and the molecules do not have orbitals of sufficient energy that are easily accessible. Thus, very reactive reagents and/or extreme reaction conditions are typically required, for example for the oxidation of alkanes. However, the initial products are almost always more reactive than the starting compounds, and undesired side reactions may occur. 

The selective functionalization of saturated hydrocarbons is an important and challenging academic and industrial objective. Our own contributions to this area are based on Gif-type systems. Recent studies have shown that fert-butyl hydroperoxide (TBHP) is an efficient oxidizing agent in these systems. 

In addition, during the course of recent mechanistic studies, new methodology for the functionalization of saturated hydrocarbons based on Gif-type protocol has been invented. These reactions are of interest as mechanistic probes and also from the point of view of synthetic utility. Thus, cycloalkanes are transformed with vaiying efficiency into mono-substituted cycloalkyl derivatives (chlorides, bromides, azides, cyanides, thiocyanates, dicycloalkyl sulfides, or nitroalkanes) by conducting iron or copper catalyzed reactions in the presence of alkali metal salts (scheme). 

The Functionalization of Saturated Hydrocarbons by Gif Chemistry. Part 1. Use of Superoxide and of Hydrogen Peroxide. Part 2. Use of t-Butylhydroperoxide (TBHP). 

Barton, D.H.R., Bevicre, S.D., Chavasiri, W., Csuhai, E., Doller, D., and Liu, W.-G. (1992) The Functionalization of Saturated Hydrocarbons. Part 20. Alkyl Hydroperoxides Reaction Intermediates in the Oxidation of Saturated Hydrocarbons by Gif-Type Reactions and Mechanistic Studies on Their Formation, Chem. Soc. 114, 2147-2156. 

Barton, D.H.R. and Chavasiri, W, (1994) Tlie Functionalization of Saturated Hydrocarbons. Part 24. The Use of ferf-Butyl Hydroperoxide GoAgg and GoAgg, Tetrahedron 50, 19-30. 

Barton DHR, May-MotherweU RS, Motherwell RB. Functionalization of saturated hydrocarbons. 1. Some reactions of a ferrous chloride chloramine-T complex with hydrocarbons. J Chem Soc Perkin Trans 1. 1983 445—451. 

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