51209-49-5Relevant academic research and scientific papers
The synthesis of perdeuterated azone (d35- 1-Dodecylhexahydro-2H-azepin-2-one)
Groundwater,Hadgraft,Harrison,Watkinson
, p. 1047 - 1053 (1994)
Perdeuteroazone (3) has been synthesised via the base-catalysed coupling of d11-hexahydro-2H-azepin-2-one (2) with d25-1-chlorododecane.
Identification of key oxidative intermediates and the function of chromium dopants in PKU-8: catalytic dehydrogenation ofsec-alcohols withtert-butylhydroperoxide
Wang, Weilu,He, Yang,He, Junkai,Dang, Yanliu,Kankanmkapuge, Tharindu,Gao, Wenliang,Cong, Rihong,Suib, Steven L.,Yang, Tao
, p. 1365 - 1374 (2021/03/14)
Catalytic oxidation reaction using green oxidants plays an important role in modern chemical engineering; however, thein situgenerated active species and the related catalytic mechanism need to be understood in depth. For this purpose, Cr-substituted aluminoborate Cr-PKU-8 catalysts were synthesized and applied as recyclable heterogeneous catalysts for the oxidation of aliphatic and aromatic alcohols usingtert-butylhydroperoxide (TBHP). Both high efficiency and selectivity (>99%) were achieved during the dehydrogenation of varioussec-alcohols into acetone in H2O solvent medium. From the analyses using isotopic tracer, molecular probe and cyclic voltammetry strategies, the chromium ions were observed to undergo a Cr3+-Cr2+-Cr3+redox cycle. DFT calculations suggest thatt-BuOO* is more energetically favourable for hydrogen abstraction fromsec-alcohol thant-BuO*, and probably acts as the key active species. Accordingly, the reaction scheme was proposed to interpret the catalytic process based on the observed results.
Mechanism of Ni-catalyzed oxidations of unactivated C(sp3)-H Bonds
Qiu, Yehao,Hartwig, John F.
supporting information, p. 19239 - 19248 (2020/11/13)
The Ni-catalyzed oxidation of unactivated alkanes, including the oxidation of polyethylenes, by meta-chloroperbenzoic acid (mCPBA) occur with high turnover numbers under mild conditions, but the mechanism of such transformations has been a subject of debate. Putative, high-valent nickel-oxo or nickel-oxyl intermediates have been proposed to cleave the C-H bond, but several studies on such complexes have not provided strong evidence to support such reactivity toward unactivated C(sp3)-H bonds. We report mechanistic investigations of Ni-catalyzed oxidations of unactivated C-H bonds by mCPBA. The lack of an effect of ligands, the formation of carbon-centered radicals with long lifetimes, and the decomposition of mCPBA in the presence of Ni complexes suggest that the reaction occurs through free alkyl radicals. Selectivity on model substrates and deuterium-labeling experiments imply that the m-chlorobenzoyloxy radical derived from mCPBA cleaves C-H bonds in the alkane to form an alkyl radical, which subsequently reacts with mCPBA to afford the alcohol product and regenerate the aroyloxy radical. This free-radical chain mechanism shows that Ni does not cleave the C(sp3)-H bonds as previously proposed; rather, it catalyzes the decomposition of mCPBA to form the aroyloxy radical.
Catalytic oxidation of water and alcohols by a robust iron(III) complex bearing a cross-bridged cyclam ligand
Tan, Peng,Kwong, Hoi-Ki,Lau, Tai-Chu
supporting information, p. 12189 - 12192 (2015/07/27)
An iron(III) complex bearing a cross-bridged cyclam ligand (4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane) is an efficient catalyst for the oxidation of both water and alcohols using sodium periodate as the oxidant. In catalytic water oxidation a maximum turnover number (TON) of 1030 is achieved, while in catalytic alcohol oxidation >95% conversions and yields can be obtained.
Efficient benzylic and aliphatic C-H oxidation with selectivity for methylenic sites catalyzed by a bioinspired manganese complex
Shen, Duyi,Miao, Chengxia,Wang, Shoufeng,Xia, Chungu,Sun, Wei
supporting information, p. 1108 - 1111 (2014/03/21)
A benzimidazole-based nonheme manganese complex efficiently catalyzes benzylic, aliphatic C-H as well as tertiary C-H oxidation with hydrogen peroxide as the oxidant in the presence of acetic acid as additive. 18O labeling experiments suggest the reaction may proceed via a high-valent manganese-oxo intermediate.
Evidence that steric factors modulate reactivity of tautomeric iron-oxo species in stereospecific alkane C-H hydroxylation
Mitra, Mainak,Lloret-Fillol, Julio,Haukka, Matti,Costas, Miquel,Nordlander, Ebbe
supporting information, p. 1408 - 1410 (2014/02/14)
A new iron complex mediates stereospecific hydroxylation of alkyl C-H bonds with hydrogen peroxide, exhibiting excellent efficiency. Isotope labelling studies provide evidence that the relative reactivity of tautomerically related oxo-iron species responsible for the C-H hydroxylation reaction is dominated by steric factors. This journal is The Royal Society of Chemistry.
Highly efficient divanadium(V) pre-catalyst for mild oxidation of liquid and gaseous alkanes
Gupta, Samik,Kirillova, Marina V.,Guedes Da Silva, M. Fátima,Pombeiro, Armando J.L.
, p. 82 - 89 (2013/07/27)
A new binuclear oxovanadium(V) complex bearing an NO2-donor Schiff base ligand, [{VO(EtO)(EtOH)}2(1κ2O,κN: 2κ2O,κN-L)]·2H2O (H4L = bis(2-hydroxybenzylidene)oxalohydrazonic acid) was prepared and fully characterized by IR, 1H NMR and electronic spectroscopies, elemental analysis and single crystal X-ray diffraction. In the presence of 2-pyrazinecarboxylic acid (PCA) or another acid promoter, this compound acts as a highly efficient pre-catalyst towards the oxidation of gaseous and liquid alkanes by aqueous H2O2 under mild conditions, in aqueous MeCN. Total yields of oxygenates up to 45% and overall turnover numbers up to 7.8 × 103 are achieved.
Alkane hydroxylation by a nonheme iron catalyst that challenges the heme paradigm for oxygenase action
Company, Anna,Gomez, Laura,Gueell, Mireia,Ribas, Xavi,Luis, Josep M.,Que Jr., Lawrence,Costas, Miquel
, p. 15766 - 15767 (2008/09/19)
A nonheme iron catalyst catalyzed stereoselective oxidation of alkanes with H2O2 with remarkable efficiency and exhibiting an unprecedented high incorporation of water into the oxidized products. The present results challenge the canonical description of oxygenases, the standard oxo-hydroxo tautomerism that applies to heme systems and serves as a precedent for alternative pathways for the oxidation of hydrocarbons at nonheme iron oxygenases. Copyright
Catalytic oxidation of C-H bonds
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Page 7 - 8, (2008/06/13)
The invention provides a catalytic, chemospecific and stereospecific method of oxidizing a wide variety of substrates without unwanted side reactions. Essentially, the method of the instant invention, under relatively mild reaction conditions, catalytically, stereospecifically and chemospecifically inserts oxygen into a hydrocarbon C—H bond. Oxidation (oxygen insertion) at a tertiary C—H bond to form an alcohol (and in some cases a hemiacetal) at the tertiary carbon is favored. The stereochemistry of an oxidized tertiary carbon is preserved. Ketones are formed by oxidizing a secondary C—H bond and ring-cleaved diones are formed by oxidizing cis tertiary CH bonds.
Chemospecific chromium[VI] catalyzed oxidation of C-H bonds at -40 °C
Lee, Seongmin,Fuchs
, p. 13978 - 13979 (2007/10/03)
H5IO6 in the presence of catalytic chromoyl diacetate is a powerful method for oxidation of C-H bonds. Tertiary and oxygen activated C-H bonds are oxidized to tertiary alcohols or ketones at temperatures as low as -40 °C. The putative reagent is neutral dioxoperoxy chromium[VI] which undergoes C-H oxidation with retention of stereochemistry. This reagent appears to be the first reagent capable of oxidation of a C-H bond in the presence of an olefin without concomitant epoxidation. Copyright
