Oxyfunctionalization of hydrocarbons

The oxidation of 3-keto steroids with O3 has also been conducted in HF-SbFs [94]. When the oxygenation of ethers was performed under similar conditions, 0x0 alkyl ethers were obtained, with the 0x0 functionality generally three carbons away from the ether linkage (Eq. 43) [95], 

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Olah, G.A. and Ohnishi. R. (1978) Oxyfunctionalization of hydrocarbons. 8. Electrophilic hydroxylation of benzene, alkylbenzenes, and halobenzenes with hydrogen peroxide in superadds. /. Org. Chem., 43, 865-867. 

The reagents are available in two steps frt SbFj [to obtain RfN=C(F)Rf ] and then wnl Oxyfunctionalization of hydrocarbons. tertiary C-H bonds by these neutral and si ceeds smoothly. 

Buehler, B., Bollhalder, L, Hauer, B., Witholt, B., and Schmid, A. (2003) Chemical biotechnology for the specific oxyfunctionalization of hydrocarbons on a technical scale. Biotechnol. Bioeng., 82, 833-842. 

Olah, G. A., A. P. Fung, and T. Keumi. 1981. Oxyfunctionalization of hydrocarbons. Hydroxylation of benzene and alkylbenzenes with hydrogen peroxide in hydrogen fluoride/boron trifluoride. J. Org. Chem. 46 4306-4307. 

R. Mello, M. Fiorentino, C. Fusco, and R. Curci, Oxidations by methyl (trifluoromethyl)-dioxirane. 2-Oxyfunctionalization of saturated hydrocarbons, J. Am. Chem. Soc., Ill (1989) 6749-6757. 

Co catalysts are used to catalyze a series of oxidations that involve one-electron redox reactions, such as oxidation of phenolic compounds, thiol oxidation, and oxyfunctionalization of saturated hydrocarbon groups. 

Curci and co-workers studied the dioxirane oxyfunctionalizations of a series of non-natural targets and found an interesting example of selective bridgehead dihydroxylation of fenestrindane 59 <1996JOC8681> and hydrocarbons bearing cyclopropyl moieties <2003JOC7806>. 

The oxyfunctionalization of linear alkanes at the terminal position is one of the major challenges of catalysis in the case of n-hexane, oxidation at the two terminal C atoms would lead to AA. However, there is a little amount of n-hexane in cracker streams, because it is easily converted to benzene. Therefore, sourcing of this hydrocarbon would be a challenge. 

This review analyzes the properties which are necessary for heterogeneous catalysts to promote the oxyfunctionalization of light paraffins to valuable chemicals. Three catalytic systems are discussed i) vanadium/phosphorus mixed oxide, the industrial catalyst for the oxidation of n-butane to maleic anhydride, which is here also examined for reactions aimed at the transformation of other hydrocarbons ii) Keggin-type heteropolycompounds, which are claimed for the oxidation of propane and isobutane, whose composition can be tuned in order to direct the reaction either to the formation of olefins or to the formation of oxygenated compounds iii) rutile-based mixed oxides, where rutile can act as the matrix for hosting transition metal ions or favour the dispersion of other metal oxides, thus promoting the different role of the various elements in the formation of acrylonitrile from propane. 

In the oxyfunctionalization of n-hexane by H2O2 (30 wt %) over titanium silicalites in methanol as a solvent [49a], the parallel-sequential reaction scheme was selected for transformation of the hydrocarbon into hexanol and hexanone ... 

Mello, R. Citttinale, F. Fiorentino, M. Fusco, C. Prencipe, T Curci, R. Oxidations by methyl(trifluoromethyl)dioxirane. 4. Oxyfunctionalization of aromatic hydrocarbons. Tetrahedron Lett. 1990, 31, 6097. 

Amone, A. Foletto, S. Metrangelo, P Pregnolato, M. Resnati, G. Highly enantiospecific oxyfunctionalization of nonactivated hydrocarbon sites by perfluoro-cfs-2- -butyl-3- -propyloxaziridine. Org. Lett. 1999,1, 281. 

Nonactivated tertiary hydrocarbon sites of enantiopure compounds 210 are oxyfunctionalized enantiospecifically by perfluoro-a.r-2- -butyl-3- -propyloxaziridine 80 under remarkably mild reaction conditions (Equation 8) <19990L281>. The reaction occurs with retention of the configuration at the oxidized stereogenic center and the enantiospecificity is highly independent of both the carbon framework of the substrate as well as functional groups (Table 16). 

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