32166-40-8Relevant academic research and scientific papers
Alkane oxidation catalysed by a self-folded multi-iron complex
Mettry, Magi,Moehlig, Melissa Padilla,Gill, Adam D.,Hooley, Richard J.
, p. 120 - 128 (2016/11/09)
A preorganised ligand scaffold is capable of coordinating multiple Fe(II) centres to form an electrophilic CH oxidation catalyst. This catalyst oxidises unactivated hydrocarbons including simple, linear alkanes under mild conditions in good yields with selectivity for the oxidation of secondary CH bonds. Control complexes containing a single metal centre are incapable of oxidising unstrained linear hydrocarbons, indicating that participation of multiple centres aids the CH oxidation of challenging substrates.
An iron catalyst for oxidation of alkyl C-H bonds showing enhanced selectivity for methylenic sites
Prat, Irene,Gomez, Laura,Canta, Merce,Ribas, Xavi,Costas, Miquel
supporting information, p. 1908 - 1913 (2013/03/14)
Many are called but few are chosen: A nonheme iron complex catalyzes the oxidation of alkyl C-H bonds by using H2O2 as the oxidant, showing an enhanced selectivity for secondary over tertiary C-H bonds (see scheme). Copyright
Mn (Br8TPPS) supported on Amberlite IRA-400 as a robust and efficient catalyst for alkene epoxidation and alkane hydroxylation
Tangestaninejad,Habibi,Mirkhani,Moghadam
, p. 264 - 270 (2007/10/03)
Manganese (III) meso-tetrakis(p-sulfonatophenyl)-β-octabromoporphyrin (supported on Amberlite IRA-400 [Mn(Br8TPPS)-Ad-400] is a robust and efficient catalyst for epoxidation of alkenes and hydroxylation of alkanes with sodium periodate at room temperature.
Oxidation with the "O2 - H2O2 - Vauauium complex - Pyrazine-2-carboxylic acid" reagent 9. Oxidation of cyclohexene and decalin
Schuchardt,Guerreiro,Shul'pin
, p. 247 - 252 (2007/11/27)
The oxidation of cyclohexene with hydrogen peroxide catalyzed by a vanadium complex and pyrazine-2-carboxylic acid (PCA) in air results in the formation of cyclohex-2-enyl hydroperoxide as the main product and cyclohex-2-enol, cyclohex-2-enone, cyclohex-3-enyl hydroperoxide, cyclohex-3-enol, cyclohexanol, cyclohexane, and 1,2-epoxycyclohexane in lesser amounts. The composition of the products of oxidation of decalin isomers with the system in question is similar to those obtained in the photochemical oxidation with hydrogen peroxide in air and in the oxidation with air in the presence of anthraquinone. A proposed mechanism for the oxidation includes the initiation by hydroxyl radicals generated from hydrogen peroxide under the action of the V - PCA system.
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.
Cascade radical mediated macrocyclisation-transannulation reactions leading to ring-fused bicycles
Pattenden, Gerald,Smithies, Allison J.,Tapolczay, David,Walter, Daryl S.
, p. 7 - 20 (2007/10/03)
The scope for tandem radical mediated macrocyclisation-transannulation processes in the elaboration of ring-fused carbocycles has been examined.Thus, a range of E-iodo dienones viz. 21, 30b, 40, 42 and 44 were first prepared using synthetic sequences based on sound literature precedent.Treatment of the iodo dienone 21 with Bu3SnH-AIBN led to a 3:2 mixture of trans- and cis-isomers of 1-decalone, 35 and 36, respectively, in a combined yield of 72percent, whereas the positional isomer 30b of 21 underwent 10-endo macrocyclisation and transannulation to a 1:1 mixture of trans-1-decalone 35 and cis-octahydroazulen-1-one 39 (combined yield 68percent), resulting from competitive 6-exo/5-exo transannular cyclisation from the intermediate cyclodecenone radical 38.In further investigations of the scope for sequential radical macrocyclisation-transannulations in the synthesis of bicyclic systems, the iodo dienone 40 was found to undergo regioselective cyclisation to the cis-tetralone 41 (50percent), whereas the iodo dienone 42 produced only (Z)-cyclooct-3-enone 54 and none of the expected bicyclooctanone 43 on treatment with Bu3SnH-AIBN.Only the 4-cyclopentylcyclohexanone 61, and none of the hoped for 7,6-bicyclic ketone 45, was produced from radical cyclisation of the iodo dienone 44.The differing reaction pathways followed by the iodo dienones 21, 30b, 40 and 42 have been rationalised in terms of the conformational preferences of the macrocyclic α-keto radical intermediates, e.g. 32, 38 and 52 involved in the various cyclisations supported by some preliminary MM2 studies and calculations.
Sequential Radical Macrocyclisation-Transannulation Approach to Ring-fused Bicycles
Pattenden, Gerald,Smithies, Allison J.,Walter, Daryl S.
, p. 2413 - 2416 (2007/10/02)
The scope for tandem radical mediated macrocyclisation-transannulation processes (Scheme 1) in the elaboration of polycycles is illustrated with the facile syntheses of linear 5,6-, 6,6- and 5,7-ring fused carbobicycles, viz 7,8,11,13 from appropriate iododienone precursors, viz 1,2,12, on treatment with Bu3SnH-AIBN
Acyl Radicals: Intermolecular and Intramolecular Alkene Addition Reactions
Boger, Dale L.,Mathvink, Robert J.
, p. 1429 - 1443 (2007/10/02)
A full study of the use of phenyl selenoesters as precursors to acyl radicals and their subsequent participation in intermolecular and intramolecular alkene addition reactions is detailed.Primary alkyl-, vinyl-, and arylsubstituted acyl radicals generated by Bu3SnH treatment of the corresponding phenyl selenoesters participate cleanly in intermolecular addition reactions with alkenes bearing electron-withdrawing or radical-stabilizing substituents at rates that exceed those of the potentially competitive decarbonylation or reduction.Similarly, their intramolecular addition to activated or unactivated alkenes proceeds without significant competitive reduction or decarbonylation and at rates generally >/= 1 x 106 s-1 with some occuring at rates >/= 3 x 107 s-1.Consistent with their behavior in intermolecular addition reactions, the 5-exo-trig cyclizations of secondary and tertiary alkyl-substituted acyl radicals to an unactivated olefin acceptor may be accompanied by varying degrees of decarbonylation, even under low-temperature free-radical conditions.Studies are presented which suggest that the intramolecular additions of acyl radicals to alkenes under the conditions detailed herein may be regarded as irreversible, kinetically controlled processes which exhibit regioselectivity that is predictable based on well-established empirical rules set forth for the analogous free-radical cyclization reactions of alkyl radicals.
Catalytic Alkane Activations in Reverse Microemulsions Containing Iron Salts and Hydrogen Peroxide
Briffaud, T.,Larpent, C.,Patin, H.
, p. 1193 - 1194 (2007/10/02)
A microemulsion system generated from two reverse microemulsions containing respectively an aqueous solution of iron salts and 30percent H2O2 dispersed in liquid alkanes catalyses the oxidation of C-H bonds.
