60159-38-8Relevant academic research and scientific papers
Oxygenation of hydrocarbons mediated by mixed-valent basic iron trifluoroacetate and valence-separated component species under Gif-type conditions involves carbon- and oxygen-centered radicals
Tapper, Amy E.,Long, Jeffrey R.,Staples, Richard J.,Stavropoulos, Pericles
, p. 2343 - 2346 (2007/10/03)
Hydrogen-atom abstraction by hydroxyl radicals takes place to generate both tert- and sec-adamantyl radicals in Gif-type oxygenation of adamantane by H2O2 in pyridine/trifluoroacetic acid when the reaction is mediated by [Fe(O2CCF3)2(py)4] or [Fe2O(O2CCF3)4(py)6], which are formed by dissociation of [Fe3O(O2CCF3)6- (L)3] in pyridine (L = H2O, DMSO; see scheme).
The selective functionalization of saturated hydrocarbons. Part 46. An investigation of Udenfriend's system under Gif conditions
Barton, Derek H.R.,Delanghe, Nathalie C.
, p. 4471 - 4476 (2007/10/03)
Under Gif conditions using ascorbic acid as reductant and oxygen as oxidant in pyridine, the selectivity for secondary hydrogen functionalization is exceptional. EDTA (ethylenediamine-tetra-acetic acid) is not needed as a ligand for iron.
The conversion of saturated hydrocarbons into carboxylic acids using Fe(CO)5-H2O2 oxidation
Barton, Derek H. R.,Delanghe, Nathalie C.
, p. 8137 - 8140 (2007/10/03)
Saturated hydrocarbons are transformed into their corresponding homologous carboxylic acids by treatment with iron pentacarbonyl and hydrogen peroxide in pyridine-acetic acid. A mechanism for this reaction is proposed. Attention is also directed to a new and convenient procedure for the determination of carbon monoxide.
The functionalization of saturated hydrocarbons. Part 24. The use of tert-butyl hydroperoxide: GoAggIV and GoAggV
Barton, Derek H. R.,Chavasiri, Warinthorn
, p. 19 - 30 (2007/10/02)
The use of tert-butyl hydroperoxide as an oxidant in Gif-type systems (GoAggIV and GoAgfV) catalyzed by various Fe(III) species is examined. Regioselectivity studids of these systems have revealed several characteristics similar to those observed for other prdviously reported Gif-type reactions. A common rdaction pathway for the GoAggIV and GoAggV oxidation systems and other Gif-type reactions (from alkane via alkyl hydroperoxide to ketone or alcohol) is seen.
The Fe(II)-Fe(IV) and Fe(III)-Fe(V) manifolds in an expanded world of gif chemistry
Bardin,Barton,Hu,Rojas-Wahl,Taylor
, p. 5805 - 5808 (2007/10/02)
The species responsible for hydrocarbon activation and formation of alkyl chlorides in the Fe(II) and Fe(III)-H2O2 and tert-butyl hydroperoxide systems are identified. The importance of the Fe(II)-Fe(IV) manifold in providing a mechanism which permits the selective functionalization of saturated hydrocarbons by ionic trapping with chloride, azide, and other anions is made manifest. Comparison is made with the Fe(III)-Fe(V) manifold where ionic trapping is never seen.
The Functionalization of Saturated Hydrocarbons. Part 26. Ionic Substitution Reactions in GoAggIV Chemistry: The Construction of C-N, C-S and C-C Bonds
Barton, Derek H. R.,Warinthorn, Chavasiri
, p. 47 - 60 (2007/10/02)
Utilization of the GoAggIV system in the presence of sodium azide, sodium nitrite, sodium thiocyanate, sodium disulfide and tetraethylammonium cyanide converts saturated hydrocarbons into the corresponding alkyl azides, nitroalkanes, alkyl thiocyanates, dialkyl disulfides and alkyl cyanides, respectively.Mechanistic studies suggest an Fe-centered ligand coupling reaction pathway.Key Words: Gif systems; Selective functionalization, Iron catalysts, C-N bond formation, C-S bond formation, C-C bond formation
The functionalization of saturated hydrocarbons. Part 25. Ionic substitution reactions in GoAggIV chemistry: The formation of carbon-halogen bonds
Barton, Derek H. R.,Beviere, Stephane D.,Chavasiri, Warinthorn
, p. 31 - 46 (2007/10/02)
GoAggIV chemistry (Fe (III) species, tert-butyl hydroperoxide in a mixture of pyridine and acetic acid) in the presence of LiCl can transform saturated hydrocarbons efficiently into the corresponding alkyl chlorides. The transformation into monosubstituted alkyl derivatives by "ionic trapping" reagents arising from the interception of the first intermediate of the system supports the presence of a high valent VFe-C species. Mechanistic studies suggest a possible pathway operating via an Fe-centered ligand coupling. In addition, the production of alkyl chlorides and alkyl bromides could also be achieved employing this system in the presence of halogenating reagents such as CCl4 and BrCCl3.
Gif-type oxidation systems. Evidence for a second intermediate between saturated hydrocarbon and ketone
Barton,Csuhai,Ozbalik
, p. 2717 - 2820 (2007/10/02)
The addition of dianisyl telluride to a Gif(IV) oxidation of adamantane has a marked effect on the ratio of ketone to secondary alcohol formed. This is interpreted as an indication of a second intermediate in the conversion of saturated hydrocarbvons into ketones. This second intermediate is probably an Fe(III) alkoxide.
Functionalization of Saturated Hydrocarbons. 14. Further Studies on the Mechanism of Gif-Type Systems
Barton, Derek H. R.,Halley, Frank,Ozbalik, Nubar,Schmitt, Martine,Young, Esme,Balavoine, Gilbert
, p. 7144 - 7149 (2007/10/02)
The photolysis (W light) of acyl derivatives of N-hydroxy-2-thiopyridone in pyridine-acetic acid permits a study of the partioning of secondary radicals between oxygen, pyridine, and the thione function.Comparison with the GifIV oxidation system for saturated hydrocarbons confirms that radicals are not involved in oxidation at secondary positions.On the contrary, radical behavior at the tertiary position in adamantane is again established.The two recently introduced Gif-type systems, GoAggI and GoAggII, have been shown to give the same overall selectivity in attack on adamantane with the usual coupling of the tertiary radical with pyridine.
