1502-24-5Relevant articles and documents
Stereoselective alkane hydroxylations by metal salts and m-chloroperbenzoic acid
Nam, Wonwoo,Ryu, Ju Yeon,Kim, Inwoo,Kim, Cheal
, p. 5487 - 5490 (2002)
Simple metal (M=Mn, Fe, Co) perchlorates associated with m-chloroperbenzoic acid are able to conduct stereoselective alkane hydroxylations via a mechanism involving metal-based oxidants; the catalytic activity of the metal salts is in the order of Co(ClO4)2>Mn(ClO4)2>Fe (ClO4)2.
Stereospecific Alkane Hydroxylation with H2O2 Catalyzed by an Iron(II)-Tris(2-pyridylmethyl)amine Complex
Kim, Cheal,Chen, Kui,Kim, Jinheung,Que, Lawrence
, p. 5964 - 5965 (1997)
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Stereoselective oxidation of alkanes with: M -CPBA as an oxidant and cobalt complex with isoindole-based ligands as catalysts
Nesterova, Oksana V.,Kopylovich, Maximilian N.,Nesterov, Dmytro S.
, p. 93756 - 93767 (2016/10/21)
Two complexes with isoindole-core ligands of general formula [M{C6H4C(NH2)NC(ONCMe2)2}2](NO3)2 (M = Co for 1 and M = Ni for 2) were studied as catalysts for the mild stereoselective alkane oxidation with m-chloroperbenzoic acid (m-CPBA) as an oxidant and cis-1,2-dimethylcyclohexane (cis-1,2-DMCH) as a main model substrate. Complex 1 disclosed a pronounced activity, with high retention of stereoconfiguration of substrates (>98% for cis-1,2-DMCH) and highest cis/trans ratio of tertiary alcohols (products) of 56, under mild conditions. The best achieved yields of tertiary cis-alcohols were of 13.7 and 50.5%, based on the substrate (cis-1,2-DMCH) and the oxidant (m-CPBA) respectively. Kinetic experiments, high bond and stereoselectivity parameters, kinetic isotope effect of 7.2(2) in the oxidation of cyclohexane, and incorporation of 18O from H218O support the involvement of CoIVO high-valent metal-oxo intermediates as main C-H attacking species.
Catalytic oxidation of alkanes by a (salen)osmium(VI) nitrido complex using H2O2 as the terminal oxidant
Chen, Man,Pan, Yi,Kwong, Hoi-Ki,Zeng, Raymond J.,Lau, Kai-Chung,Lau, Tai-Chu
supporting information, p. 13686 - 13689 (2015/09/02)
The osmium(vi) nitrido complex, [OsVI(N)(L)(CH3OH)]+ (1, L = N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion) is an efficient catalyst for the oxidation of alkanes under ambient conditions using H2O2 as the oxidant. Alkanes are oxidized to the corresponding alcohols and ketones, with yields up to 75% and turnover numbers up to 2230. Experimental and computational studies are consistent with a mechanism that involves O-atom transfer from H2O2 to [OsVI(N)(L)]+ to generate an [OsVIII(N)(O)(L)]+ active intermediate.
Highly efficient alkane oxidation catalyzed by [MnV(N)(CN) 4]2-. Evidence for [MnVII(N)(O)(CN) 4]2- as an active intermediate
Ma, Li,Pan, Yi,Man, Wai-Lun,Kwong, Hoi-Ki,Lam, William W.Y.,Chen, Gui,Lau, Kai-Chung,Lau, Tai-Chu
, p. 7680 - 7687 (2014/06/10)
The oxidation of various alkanes catalyzed by [MnV(N)(CN) 4]2- using various terminal oxidants at room temperature has been investigated. Excellent yields of alcohols and ketones (>95%) are obtained using H2O2 as oxidant and CF3CH 2OH as solvent. Good yields (>80%) are also obtained using (NH4)2[Ce(NO3)6] in CF 3CH2OH/H2O. Kinetic isotope effects (KIEs) are determined by using an equimolar mixture of cyclohexane (c-C6H 12) and cyclohexane-d12 (c-C6D12) as substrate. The KIEs are 3.1 ± 0.3 and 3.6 ± 0.2 for oxidation by H2O2 and Ce(IV), respectively. On the other hand, the rate constants for the formation of products using c-C6H12 or c-C6D12 as single substrate are the same. These results are consistent with initial rate-limiting formation of an active intermediate between [Mn(N)(CN)4]2- and H2O2 or CeIV, followed by H-atom abstraction from cyclohexane by the active intermediate. When PhCH2C(CH3)2OOH (MPPH) is used as oxidant for the oxidation of c-C6H12, the major products are c-C6H11OH, c-C6H10O, and PhCH2C(CH3)2OH (MPPOH), suggesting heterolytic cleavage of MPPH to generate a Mn=O intermediate. In the reaction of H2O2 with [Mn(N)(CN)4]2- in CF 3CH2OH, a peak at m/z 628.1 was observed in the electrospray ionization mass spectrometry, which is assigned to the solvated manganese nitrido oxo species, (PPh4)[Mn(N)(O)(CN)4] -·CF3CH2OH. On the basis of the experimental results the proposed mechanism for catalytic alkane oxidation by [MnV(N)(CN)4]2-/ROOH involves initial rate-limiting O-atom transfer from ROOH to [Mn(N)(CN)4]2- to generate a manganese(VII) nitrido oxo active species, [MnVII(N)(O) (CN)4]2-, which then oxidizes alkanes (R'H) via a H-atom abstraction/O-rebound mechanism. The proposed mechanism is also supported by density functional theory calculations.
