- Synthesis of adamantane-based trimeric cationic surfactants
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Three trimeric quaternary ammonium surfactants, having adamantane cores and different carbon chains, were synthesized using adamantane as the starting raw material. The target compounds were confirmed by elemental analysis, 1H NMR, 13C NMR, and mass spectroscopy. The influences of reaction conditions on the yields of the key intermediate product 1,3,5-trihydroxyadamantane (3) were investigated. Surface properties of the target compounds were measured. The critical micelle concentration values of 1a, 1b, and 1c were 2mM, 1mM, and 0.5mM, respectively.
- Zhu, Hua,Guo, Jianwei,Yang, Chufen,Liu, Sa,Cui, Yingde,Zhong, Xing
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- Oxidations by methyl(trifluoromethyl) dioxirane. 3. Selective polyoxyfunctionalization of adamantane
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Adamantane (1) can be converted directly into adamantan-1,3,5-triol (5) and into adamantan-1,3,5,7-tetraol (6) under remarkably mild conditions by employing an excess of isolated methyl (trifluoromethyl)dioxirane (3a) in solution. This new dioxirane species was found to be over 7,000-fold more reactive than dimethyldioxirane (3b) in performing adamantane hydroxylations.
- Mello, Rossella,Cassidei, Luigi,Fiorentino, Michele,Fusco, Caterina,Curci, Ruggero
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- Photoassisted oxygenation of alkane catalyzed by ruthenium complexes using 2,6-dichloropyridine N-oxide under visible light irradiation
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The chloro(Me2SO)ruthenium(II) complexes with tris(2-pyridylmethyl)amine or its derivative catalyses the selective, stereospecific, and photoregulative alkane oxidation in the presence of 2,6-dichloropyridine N-oxide under visible light irradiation.
- Yamaguchi, Motowo,Kumano, Takashi,Masui, Dai,Yamagishi, Takamichi
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- Synthesis and properties of novel cationic gemini surfactants with adamantane spacer
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Novel quaternary ammonium cationic gemini surfactants, with two hydrocarbon chains and an adamantane core, were designed and synthesized by three-step reactions from adamantane. The structure of obtained surfactants were confirmed by 1H NMR, FTIR and elements analysis and the surface properties of these surfactants were also studied by surface tension measurements. These target surfactants exhibit much lower critical micelle concentrations (CMC) and higher efficiency in lowering the surface tension of water than typical surfactants.
- Xu, Xiao-Jian,Guo, Jian-Wei,Zhong, Xing
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- Selective biohydroxylation of 1-substituted adamantanes using Absidia cylindrospora (I.M.I. 342950)
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The biohydroxylation of 1-substituted adamantanes using Absidia cylindrospora in a whole-cell oxidation system exclusively generated 3-hydroxy and 4ax-hydroxy derivatives; the assignments were confirmed by three X-ray crystal structure determinations.
- Bailey, Patrick D.,Higgins, Stanley D.,Ridyard, Colin H.,Roberts, Stanley M.,Rosair, Georgina M.,Whittaker, Roger A.,Willetts, Andrew J.
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- Hydroxylation of polycyclic alkanes with molecular oxygen catalyzed by N-hydroxyphthalimide (NHPI) combined with transition metal salts
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Adamantanes were successfully converted into the corresponding mono- and dihydroxy adamantanes with molecular oxygen in the presence of N- hydroxyphthalimide (NHPI) combined with cobalt salts under mild conditions. For example, exposure of adamantane under oxygen atmosphere in the presence of NHPI (10 mol%) and Co(acac)2 (0.5 mol%) in acetic acid at 75 °C for 6 h afforded adamantan-1-ol (43 %) and adamantane-1,3-diol (40 %) along with adamantan-2-one (8 %) in 93 % conversion. Similarly, 1,3-dimethyladamantane produced 3,5-dimethyladamantan-1-ol (47 %) and 5,7-dimethyladamantane-1,3- diol (37 %).
- Ishii, Yasutaka,Kato, Susumu,Iwahama, Takahiro,Sakaguchi, Satoshi
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- Ruthenium-Immobilized Periodic Mesoporous Organosilica: Synthesis, Characterization, and Catalytic Application for Selective Oxidation of Alkanes
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Periodic mesoporous organosilica (PMO) is a unique material that has a crystal-like wall structure with coordination sites for metal complexes. A Ru complex, [RuCl2(CO)3]2, is successfully immobilized onto 2,2'-bipyridine (BPy) units of PMO to form a single-site catalyst, which has been confirmed by various physicochemical analyses. Using NaClO as an oxidant, the Ru-immobilized PMO oxidizes the tertiary C-H bonds of adamantane to the corresponding alcohols at 57 times faster than the secondary C-H bonds, thereby exhibiting remarkably high regioselectivity. Moreover, the catalyst converts cis-decalin to cis-9-decalol in a 63% yield with complete retention of the substrate stereochemistry. The Ru catalyst can be separated by simple filtration and reused without loss of the original activity and selectivity for the oxidation reactions.
- Ishito, Nobuhiro,Kobayashi, Hirokazu,Nakajima, Kiyotaka,Maegawa, Yoshifumi,Inagaki, Shinji,Hara, Kenji,Fukuoka, Atsushi
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- RUTHENIUM COMPLEX AND PRODUCTION METHOD THEREOF, CATALYST, AND PRODUCTION METHOD OF OXYGEN-CONTAINING COMPOUND
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PROBLEM TO BE SOLVED: To provide a ruthenium complex that is particularly useful as a catalyst for oxidizing a substrate having a carbon-hydrogen bond. SOLUTION: The ruthenium complex represented by the general formula (i) or a cis conformer thereof is provided. In the general formula (i), R1 represents H, a phenyl group or a substituted phenyl group; R2 represents H, a phenyl group or an alkyl group; L1 represents halogen or water molecule; L2 represents triphenylphosphine, pyridine, imidazole or dimethylsulfoxide; X represents halogen; and n represents 1 or 2. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPO&INPIT
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Paragraph 0086-0097
(2021/01/29)
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- Method for preparing 1,3-adamantane diol by taking 1-bromo-adamantane as initial raw material
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The invention discloses a method for preparing 1,3-adamantane diol by taking 1-bromo-adamantane as an initial raw material, which comprises the following steps: (1) dissolving 1-bromo-adamantane in anorganic solvent, and adding concentrated sulfuric acid and nitric acid to carry out nitration reaction, thereby obtaining an organic solution phase; and (2) mixing the obtained organic solution phasewith a water solution of a strong base, and carrying out a hydrolysis reaction to obtain the product. According to the method, the 1,3-adamantane diol is synthesized by taking 1-bromo-adamantane which is easily available and low in cost as an initial raw material, so that the defects of high production cost and complex separation and purification of a target product in an existing industrial production process taking the 1,3-dibromo adamantane as a raw material are overcome; particularly, the mixed acid phase and the alkaline water liquid phase can be recycled and adjusted for multiple times,so that the environment-friendly treatment cost of the production waste is greatly reduced.
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Paragraph 0085-0090
(2021/01/25)
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- Method for preparing 1,3-adamantanediol by taking 1-adamantanol as initial raw material
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The invention discloses a method for preparing 1,3-adamantanediol by using 1-adamantanol as an initial raw material. The method comprises the following steps: (1) mixing 1-adamantanol with a mixed acid solution of fuming sulfuric acid, acetic anhydride and nitric acid, carrying out nitration reaction, and diluting the reacted material with clear water to terminate the reaction; (2) heating the material water liquid after the nitration reaction is ended, and introducing gas; (3) adding powdery activated carbon into the termination material into which the gas is introduced, adding clear water tofurther dilute the sulfuric acid solution, and separating precipitates from the acid solution; and (4) mixing the precipitate separated in the step (3) with strong base, alkalizing and hydrolyzing toobtain the product. The method has the advantages of easily available initial raw materials, high product yield, low production cost, safety, environmental protection, and facilitation of industrialpromotion and application.
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Paragraph 0053-0118
(2021/01/29)
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- Catalytic Highly Regioselective C-H Oxygenation Using Water as the Oxygen Source: Preparation of 17O/18O-Isotope-Labeled Compounds
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We found that the oxygen atom of water is activated to iodosylbenzene derivatives via reversible hydrolysis of PhI(OOCR)2 and can be used to the oxygen source for ruthenium(bpga)-catalyzed site-selective C-H oxygenation. Ru(bpga)/PhI(OOCR)2/H2O system, sterically less bulky methinic and methylenic C-H bonds in various compounds can be converted to desired oxygen functional groups in a site-selective manner. Using this method, oxygen-isotope labeled compounds such as d-[3-17O/18O]-mannose can be prepared in a multigram scale.
- Doiuchi, Daiki,Uchida, Tatsuya
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supporting information
p. 7301 - 7305
(2021/10/01)
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- Preparation method of 1, 3-dihydroxy adamantane
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The invention belongs to the technical field of organic synthesis, and discloses a preparation method of 1, 3-dihydroxy adamantane, which comprises the following steps: dissolving adamantane in a solvent, adding a nitroxide free radical catalyst and a cocatalyst, adding hypochlorite under alkaline conditions, and carrying out oxidation and purification treatment to obtain 1, 3-dihydroxy adamantane. The synthetic route is simple, and the nitroxide free radical catalyst and the cocatalyst are used in cooperation, so that the product yield is high.
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Paragraph 0024-0030
(2021/04/17)
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- Efficient alkane hydroxylation catalysis of nickel(ii) complexes with oxazoline donor containing tripodal tetradentate ligands
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Tris(oxazolynylmethyl)amine TOAR(where R denotes the substituent groups on the fourth position of the oxazoline rings) complexes of nickel(ii) have been synthesized as catalyst precursors for alkane oxidation withmeta-chloroperoxybenzoic acid (m-CPBA). The molecular structures of acetato, nitrato,meta-chlorobenzoato and chlorido complexes with TOAMe2have been determined using X-ray crystallography. The bulkiness of the substituent groups R affects the coordination environment of the nickel(ii) centers, as has been demonstrated by comparison of the molecular structures of chlorido complexes with TOAMe2and TOAtBu. The nickel(ii)-acetato complex with TOAMe2is an efficient catalyst precursor compared with the tris(pyridylmethyl)amine (TPA) analogue. Oxazolynyl donors’ strong s-electron donating ability will enhance the catalytic activity. Catalytic reaction rates and substrate oxidizing position selectivity are controlled by the structural properties of the R of TOAR. Reaction of the acetato complex with TOAMe2andm-CPBA yields the corresponding acylperoxido species, which can be detected using spectroscopy. Kinetic studies of the decay process of the acylperoxido species suggest that the acylperoxido species is a precursor of an active species for alkane oxidation.
- Hikichi, Shiro,Horii, Sena,Nakazawa, Jun,Okamura, Masaya,Terao, Ikumi
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p. 6108 - 6118
(2020/05/25)
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- Non-Heme-Type Ruthenium Catalyzed Chemo- and Site-Selective C?H Oxidation
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Herein, we developed a Ru(II)(BPGA) complex that could be used to catalyze chemo- and site-selective C?H oxidation. The described ruthenium complex was designed by replacing one pyridyl group on tris(2-pyridylmethyl)amine with an electron-donating amide ligand that was critical for promoting this type of reaction. More importantly, higher reactivities and better chemo-, and site-selectivities were observed for reactions using the cis-ruthenium complex rather than the trans-one. This reaction could be used to convert sterically less hindered methyne and/or methylene C?H bonds of a various organic substrates, including natural products, into valuable alcohol or ketone products.
- Doiuchi, Daiki,Nakamura, Tatsuya,Hayashi, Hiroki,Uchida, Tatsuya
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supporting information
p. 762 - 765
(2020/03/05)
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- Chemoselectivity of Nitroxylation of Cage Hydrocarbons
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Abstract: The composition of reaction mixtures obtained by nitroxylation of 13 cage hydrocarbons with 100% nitric acid and its mixtures with acetic acid, acetic anhydride, and methylene chloride has been studied. More reactive substrates react with lowest
- Ivleva, E. A.,Klimochkin, Yu. N.,Leonova, M. V.
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p. 1702 - 1710
(2020/12/01)
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- Direct Oxidation of Csp3?H bonds using in Situ Generated Trifluoromethylated Dioxirane in Flow
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A fast, scalable, and safer Csp3?H oxidation of activated and un-activated aliphatic chains can be enabled by methyl(trifluoromethyl)dioxirane (TFDO). The continuous flow platform allows the in situ generation of TFDO gas and its rapid reactivity toward tertiary and benzylic Csp3?H bonds. The process exhibits a broad scope and good functional group compatibility (28 examples, 8–99 %). The scalability of this methodology is demonstrated on 2.5 g scale oxidation of adamantane.
- Lesieur, Mathieu,Battilocchio, Claudio,Labes, Ricardo,Jacq, Jér?me,Genicot, Christophe,Ley, Steven V.,Pasau, Patrick
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supporting information
p. 1203 - 1207
(2019/01/04)
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- Efficient Aliphatic C?H Bond Oxidation Catalyzed by Manganese Complexes with Hydrogen Peroxide
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A tetradentate nitrogen ligand containing a benzimidazole ring and an electron-rich pyridine ring was developed, the resulting manganese complex exhibited good activity in the C?H oxidation of simple alkanes. In particular, cyclic aliphatic alkanes were transformed into ketones in very good yields (up to 89 %) by using environmentally benign H2O2 as the terminal oxidant. This protocol was also applied successfully in benzylic C?H oxidation, giving the corresponding ketones with very good selectivities. In addition, tertiary C?H bond oxidation of complex molecules by the manganese complex showed potential utility for assembling alcohols with good selectivity in late-stage chemical synthesis.
- Wang, Wenfang,Xu, Daqian,Sun, Qiangsheng,Sun, Wei
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supporting information
p. 2458 - 2464
(2018/04/02)
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- Cis -Oxoruthenium complexes supported by chiral tetradentate amine (N4) ligands for hydrocarbon oxidations
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We report the first examples of ruthenium complexes cis-[(N4)RuIIICl2]+ and cis-[(N4)RuII(OH2)2]2+ supported by chiral tetradentate amine ligands (N4), together with a high-valent cis-dioxo complex cis-[(N4)RuVI(O)2]2+ supported by the chiral N4 ligand mcp (mcp = N,N′-dimethyl-N,N′-bis(pyridin-2-ylmethyl)cyclohexane-1,2-diamine). The X-ray crystal structures of cis-[(mcp)RuIIICl2](ClO4) (1a), cis-[(Me2mcp)RuIIICl2]ClO4 (2a) and cis-[(pdp)RuIIICl2](ClO4) (3a) (Me2mcp = N,N′-dimethyl-N,N′-bis((6-methylpyridin-2-yl)methyl)cyclohexane-1,2-diamine, pdp = 1,1′-bis(pyridin-2-ylmethyl)-2,2′-bipyrrolidine)) show that the ligands coordinate to the ruthenium centre in a cis-α configuration. In aqueous solutions, proton-coupled electron-transfer redox couples were observed for cis-[(mcp)RuIII(O2CCF3)2]ClO4 (1b) and cis-[(pdp)RuIII(O3SCF3)2]CF3SO3 (3c′). Electrochemical analyses showed that the chemically/electrochemically generated cis-[(mcp)RuVI(O)2]2+ and cis-[(pdp)RuVI(O)2]2+ complexes are strong oxidants with E° = 1.11-1.13 V vs. SCE (at pH 1) and strong H-atom abstractors with DO-H = 90.1-90.8 kcal mol-1. The reaction of 1b or its (R,R)-mcp counterpart with excess (NH4)2[CeIV(NO3)6] (CAN) in aqueous medium afforded cis-[(mcp)RuVI(O)2](ClO4)2 (1e) or cis-[((R,R)-mcp)RuVI(O)2](ClO4)2 (1e?), respectively, a strong oxidant with E(RuVI/V) = 0.78 V (vs. Ag/AgNO3) in acetonitrile solution. Complex 1e oxidized various hydrocarbons, including cyclohexane, in acetonitrile at room temperature, affording alcohols and/or ketones in up to 66% yield. Stoichiometric oxidations of alkenes by 1e or 1e? in tBuOH/H2O (5:1 v/v) afforded diols and aldehydes in combined yields of up to 98%, with moderate enantioselectivity obtained for the reaction using 1e?. The cis-[(pdp)RuII(OH2)2]2+ (3c)-catalysed oxidation of saturated C-H bonds, including those of ethane and propane, with CAN as terminal oxidant was also demonstrated.
- Tse, Chun-Wai,Liu, Yungen,Wai-Shan Chow, Toby,Ma, Chaoqun,Yip, Wing-Ping,Chang, Xiao-Yong,Low, Kam-Hung,Huang, Jie-Sheng,Che, Chi-Ming
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p. 2803 - 2816
(2018/03/21)
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- Liquid-phase oxidation of alkanes with molecular oxygen catalyzed by high valent iron-based perovskite
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Hexagonal BaFeO3-δ containing high valent iron species acted as an efficient heterogeneous catalyst for the aerobic oxidation of alkanes without the need for additives. The activity of BaFeO3-δ was much higher than that of typical Fe3+/Fe2+-containing iron oxide-based catalysts, and the recovered catalyst could be reused without significant loss of catalytic performance.
- Shibata, Satomi,Sugahara, Kosei,Kamata, Keigo,Hara, Michikazu
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supporting information
p. 6772 - 6775
(2018/06/26)
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- Stereospecific sp3 C–H oxidation with m-CPBA: A CoIII Schiff base complex as pre-catalyst vs. its CoIIICdII heterometallic derivative
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The mono- and binuclear Schiff base complexes [CoL3]·DMF (1) and [CoCdL3Cl2]·0.5H2O (2) were facilely synthesized using zerovalent cobalt and cadmium chloride (for 2) as starting materials and the pre-formed pro-ligand HL (2-methoxy-6-[(methylimino)methyl]phenol, the product of condensation of o-vanillin and methylamine) in air. The compounds were characterized by single crystal X-ray diffraction analysis and spectroscopic methods in solution and in the solid state. Both complexes demonstrate a profound catalytic activity in the stereoselective oxidation of cis-1,2-dimethylcyclohexane (model substrate) with m-CPBA (m-chloroperbenzoic acid) under mild conditions in the presence of promoters of various acidity (HNO3, TFA and HOAc). The heterometallic binuclear CoIIICdII pre-catalyst (2) was more active than the mononuclear CoIII one (1), exhibiting higher products yields up to 51% and excellent stereospecificity (up to 99.2% retention of stereoconfiguration). This result could be associated with a synergistic effect of two different metals in 2. Based on the large obtained kinetic isotope effect and H218O labeling studies, the overall reaction mechanism was proposed to proceed without the participation of free alkyl radicals. The acidity of the promoter was shown to influence catalytic parameters for both 1 and 2 so that the better parameters are achieved with the acid possessing lower pKa values (a stronger acid). The comparison of the catalytic behaviours of 1 and 2 is discussed in detail considering relevant examples from the literature.
- Nesterova, Oksana V.,Kasyanova, Katerina V.,Makhankova, Valeriya G.,Kokozay, Vladimir N.,Vassilyeva, Olga Yu.,Skelton, Brian W.,Nesterov, Dmytro S.,Pombeiro, Armando J.L.
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p. 171 - 184
(2018/05/28)
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- Synthesis and biological evaluation of memantine nitrates as a potential treatment for neurodegenerative diseases
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A series of memantine nitrate derivatives, as dual functional compounds with neuroprotective and vasodilatory activity for neurodegenerative diseases, was designed and synthesized. These compounds combined the memantine skeleton and a nitrate moiety, and thus inhibited the N-methyl-d-aspartic acid receptor and released NO in the central nervous system. The biological evaluation results revealed that the new memantine nitrates were effective in protecting neurons against glutamate-induced injury in vitro. Moreover, memantine nitrates dilated aortic rings against phenylephrine-induced contraction. The structure-activity relationships of neuroprotection and vasodilation were both analyzed. In further studies, compound MN-05 significantly protected cortical neurons by inhibiting Ca2+ influx, reducing free radical production and maintaining the mitochondrial membrane potential. Further research on MN-05 is warranted.
- Liu, Zheng,Yang, Si,Jin, Xiaoyong,Zhang, Gaoxiao,Guo, Baojian,Chen, Haiyun,Yu, Pei,Sun, Yewei,Zhang, Zaijun,Wang, Yuqiang
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supporting information
p. 135 - 147
(2017/02/05)
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- Organocatalytic, Dioxirane-Mediated C-H Hydroxylation under Mild Conditions Using Oxone
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Dioxiranes are among the most selective and useful reagents for C(sp3)-H hydroxylation, but the development of a general dioxirane-mediated catalytic method has been an elusive goal. A trifluoromethyl ketone catalyst in combination with Oxone is shown to enable the first dioxirane-mediated catalytic hydroxylations that approximate the reactivity and selectivity of isolated dioxiranes. The mild reaction conditions allow for selective 3° hydroxylation and 2° oxidation and are tolerant of acid-sensitive functionality and electron-neutral arenes.
- Shuler, William G.,Johnson, Shea L.,Hilinski, Michael K.
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supporting information
p. 4790 - 4793
(2017/09/22)
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- One-pot synthesis of cage alcohols
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An efficient one-pot procedure has been developed for the synthesis of cage alcohols with hydroxy groups in the bridgehead positions. The procedure includes initial nitroxylation with nitric acid or a mixture of nitric acid with acetic acid and subsequent hydrolysis in the presence of urea.
- Klimochkin, Yu. N.,Yudashkin,Zhilkina,Ivleva,Moiseev,Oshis, Ya. F.
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p. 971 - 976
(2017/09/07)
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- Stereoselective oxidation of alkanes with: M -CPBA as an oxidant and cobalt complex with isoindole-based ligands as catalysts
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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.
- Nesterova, Oksana V.,Kopylovich, Maximilian N.,Nesterov, Dmytro S.
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p. 93756 - 93767
(2016/10/21)
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- Synthesis of hydroxy derivatives from adamantanecarboxylic acids in the system MnO2–H2SO4
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A convenient procedure has been developed for the synthesis of mono- and dihydric cage alcohols from adamantanecarboxylic acids and their esters using the MnO2–H2SO4system. The reaction at elevated temperature involved both decarboxylation and decarbonylation of the initial acid or ester.
- Ivleva,Gavrilova,Klimochkin, Yu. N.
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p. 785 - 790
(2016/07/30)
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- Improved approach towards synthesis of adamantane-1,3,5-triol
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1-Adamantanol can be converted into adamantane-1,3,5-triol in the presence of N-hydroxylphthtalimide, cobalt(II) acetylacetonate, and manganese dioxide under oxygen atmosphere in glacial acetic acid.
- Ivleva,Platonov,Klimochkin
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p. 1830 - 1833
(2015/10/12)
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- Chemoselective hydroxylation of aliphatic sp3 C-H bonds using a ketone catalyst and aqueous H2O2
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The first ketone-catalyzed method for the oxidation of aliphatic C-H bonds is reported. The reaction conditions employ aryl trifluoromethyl ketones in catalytic amounts and hydrogen peroxide as the terminal oxidant. Hydroxylation is stereospecific and chemoselective for tertiary over secondary C-H bonds. A catalytic cycle invoking a dioxirane as the active oxidant is proposed.
- Pierce, Conor J.,Hilinski, Michael K.
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supporting information
p. 6504 - 6507
(2015/01/16)
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- COMPOUNDS CONTAINING AN ALICYCLIE STRUCTURE AND ANTI-TUMOR APPLICATION
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This invention relates with anti-tumor activities of new compounds containing an adamantyl group or analogs thereof. The invention also relates with the medication applications of anti-tumor and other diseases by this kind of compounds with the combination of S, P, T structures containing adamantyl group and the formation of stereoisomer, tautomers, prodrug, pharmaceutically acceptable salts, complex salts or solvates to their anticancer application and anticancer agents, which have the following general formula:
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Paragraph 0049
(2014/03/21)
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- Electronic tuning of iron-oxo-mediated C-H activation: Effect of electron-donating ligand on selectivity
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We have reported previously that an iron(III) complex supported by an anionic pentadentate monoamido ligand, dpaqH (dpaq H=2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamido), promotes selective C-H hydroxylation with H2O2 with high regioselectivity. Herein, we report on the preparation of FeIII-dpaq derivatives that have a series of substituent groups at the 5-position of a quinoline moiety in the parent ligand dpaqH (dpaqR, R: OMe, H, Cl, and NO2), and examine them with respect to their catalytic activity in C-H hydroxylation with H2O2. As the substituent group becomes more electron-withdrawing, both the selectivity and the turnover number increase, but the selectivity of epoxidation shows the opposite trend. Copyright
- Hitomi, Yutaka,Arakawa, Kengo,Kodera, Masahito
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supporting information
p. 14697 - 14701
(2013/11/06)
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- Selective oxidation of unactivated C-H bonds by supramolecular control
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Efficient methods for dioxirane-based selective C-H bond oxidation by supramolecular control in H2O have been developed. With β-cyclodextrin as the supramolecular host, site-selective oxidation of the terminal over the internal tertiary C-H bond of 3,7-dimethyloctyl esters 3a-c was achieved. In addition, β-cyclodextrin selectively enhanced the C-H bond oxidation of cumene in a mixture of cumene and ethyl benzene in H2O. Through 1H NMR studies, the selectivity in C-H bond oxidation could be attributed to the inclusion complex formation between β-cyclodextrin and the substrates. The Royal Society of Chemistry 2012.
- Fung, Yat-Sing,Yan, Siu-Cheong,Wong, Man-Kin
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supporting information; experimental part
p. 3122 - 3130
(2012/05/07)
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- Oxidative functional group transformations with hydrogen peroxide catalyzed by a divanadium-substituted phosphotungstate
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A divanadium-substituted phosphotungstate TBA4[γ-PW 10O38V2(μ-OH)(μ-O)] (I, TBA = tetra-n-butylammonium) reacts with one equivalent H+ to form a bis-μ-hydroxo species [γ-PW10O38V 2(μ-OH)2]3- (I′) in organic media. The strong electrophilic oxidants such as [γ-PW10O 38V2(μ-OH)(μ-OOH)]3- (II) and [γ-PW10O38V2(μ-η2: η2-O2)]3- (III) are formed by the reaction of the bis-μ-hydroxo species with H2O2. In the presence of I and H+, H2O2-based oxidations such as (i) epoxidation of alkenes (17 examples including electron-deficient ones), (ii) hydroxylation of alkanes (11 examples), and (iii) oxidative bromination of alkenes, alkynes, and aromatics with Br- as a bromo source (12 examples including chlorination) chemo-, diastereo-, and regioselectively proceed to give the corresponding oxidized products in moderate to high yields with high efficiencies of H2O2 utilization.
- Mizuno, Noritaka,Kamata, Keigo,Yamaguchi, Kazuya
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scheme or table
p. 157 - 161
(2012/06/18)
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- Effective oxidation of benzylic and alkane C-H bonds catalyzed by sodium o-iodobenzenesulfonate with Oxone as a terminal oxidant under phase-transfer conditions
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Catalytic oxidation of benzylic C-H bonds could be efficiently realized using IBS as a catalyst which was generated in situ from the oxidation of sodium 2-iodobenzenesulfonate (1b) by Oxone in the presence of a phase-transfer catalyst, tetra-n-butylammonium hydrogen sulfate, in anhydrous acetonitrile at 60 °C. Various alkylbenzenes, including toluenes and ethylbenzenes, several oxygen-containing functionalities substituted alkylbenzenes, and a cyclic benzyl ether could be efficiently oxidized. And, the same reagent system of cat. 1b/Oxone/cat. n-Bu4NHSO4 could be applied to the effective oxidation of alkanes as well.
- Cui, Li-Qian,Liu, Kai,Zhang, Chi
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experimental part
p. 2258 - 2265
(2011/05/08)
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- Metal-free activation of dioxygen by graphene/g-C3N4 nanocomposites: Functional dyads for selective oxidation of saturated hydrocarbons
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Graphene sheet/polymeric carbon nitride nanocomposite (GSCN) functions as a metal-free catalyst to activate O2 for the selective oxidation of secondary C-H bonds of cyclohexane. By fine-tuning the weight ratio of graphene and carbon nitride components, GSCN offers good conversion and high selectivity to corresponding ketones. Besides its high stability, this catalyst also exhibits high chemoselectivity for secondary C-H bonds of various saturated alkanes and, therefore, should be useful in overcoming challenges confronted by metal-mediated catalysis.
- Li, Xin-Hao,Chen, Jie-Sheng,Wang, Xinchen,Sun, Jianhua,Antonietti, Markus
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scheme or table
p. 8074 - 8077
(2011/07/08)
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- PROCESS FOR PRODUCTION OF OXYGEN-CONTAINING ORGANIC COMPOUND
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Disclosed is a process for the production of an oxygen-containing organic compound by oxidizing an organic compound with molecular oxygen in a liquid phase in the presence both of a catalytic nitrogen-containing cyclic compound and a catalyst including a solid superacid and, supported thereon, a transition metal compound, in which the nitrogen-containing cyclic compound contains, as a ring constituent, a skeleton represented by following Formula (1), wherein X represents an -OR group, and wherein R represents hydrogen atom or a hydroxyl-protecting group. The process gives the oxygen-containing organic compound in a high yield and enables easy recovery and reuse of the catalyst.
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Page/Page column 18
(2010/11/19)
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- Selective hydroxylation of adamantane and its derivatives
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A general method was developed for hydroxylation into the nodal position of adamantane and its 1- and 2-substituted derivatives employing systems H 2O-CBr4 (BrCCl3, CCl4) in the presence of complexes of Pd, Ni, Ru, Co, Mo, W, and Fe. The oxidants in the systems are hypochlorous (HOCl) or hypobromous (HOBr) acids generated from water and halomethanes under the reaction conditions.
- Khusnutdinov,Shchadneva,Mukhametshina,Dzhemilev
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scheme or table
p. 1137 - 1142
(2009/12/03)
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- A free radical process for oxidation of hydrocarbons promoted by nonmetal xanthone and tetramethylammonium chloride under mild conditions
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A nonmetal catalytic system consisting of N-hydroxyphthalimide, xanthone, and tetramethylammonium chloride was developed. A wide range of hydrocarbons could be oxidized efficiently with dioxygen under mild conditions. In the presence of xanthone and tetramethylammonium chloride, catalytic activity of N-hydroxyphthalimide was greatly improved, and selectivity for alkyl hydroperoxide was remarkably decreased.
- Du, Zhongtian,Sun, Zhiqiang,Zhang, Wei,Miao, Hong,Ma, Hong,Xu, Jie
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supporting information; experimental part
p. 1677 - 1680
(2009/09/05)
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- ALCOHOL OXIDATION CATALYST AND METHOD OF SYNTHESIZING THE SAME
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An organic oxidation catalyst for alcohols which is environmentally less harmful and with which efficient oxidation can be conducted. The oxidation catalyst for alcohols is a 1-alkyl-2-azadamantan-N-oxyl which has a nitroxyl group incorporated in the adamantane skeleton and was synthesized from as a base material a bicyclic compound obtained by the Grob-type ring-opening reaction of 1,3-adamantanediol. Due to the nitroxyl group on the adamantane skeleton, the ±-position hydrogen is stabilized based on Bredt's rule and the stability of the oxoammonium group generated by the oxidation thereof is ensured. Compared to TEMPO, which is a conventional oxidation catalyst, this catalyst is reduced in steric hindrance and is usable in a wide range of reaction fields. Because of this, not only a primary alcohol but a secondary alcohol having a sterically complicated structure, which has been difficult to oxidize with TEMPO, can be oxidized at a high efficiency.
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Page/Page column 10; 10-11; 18; 19
(2008/06/13)
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- Process for producing oxygen-bearing compound
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Provided is a process for industrially advantageously producing an oxygen-bearing compound (e.g., an alcohol, a diol, a polyol, or a ketone) through oxidation of an alkane or an alcohol, which process requires no treatment for separation/removal of a catalyst and causes no equipment corrosion. Specifically, there are provided a process for producing an oxygen-bearing compound, including oxidizing an alkane in the presence of a catalyst containing at least one element selected from among transition metal elements belonging to Groups 5 and 8 to 10 of the periodic table, wherein the oxygen-bearing compound is an alcohol, a diol, a polyol, or a ketone; and a process for producing an oxygen-bearing compound, including oxidizing an alcohol in the presence of a catalyst containing at least one element selected from among transition metal elements belonging to Groups 5 and 8 to 10 of the periodic table, wherein the oxygen-bearing compound is a diol, a polyol, or a ketone.
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Page/Page column 6-7
(2008/06/13)
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- Selective oxidation of alkanes with molecular oxygen and acetaldehyde in compressed (supercritical) carbon dioxide as reaction medium
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The oxidation of cycloalkanes or alkylarenes with molecular oxygen and acetaldehyde as sacrificial co-reductant occurs efficiently in compressed (supercritical) carbon dioxide (scCO2) under mild multiphase conditions. No catalyst is required and high-pressure ATR-FTIR online measurements show that a radical reaction pathway is heterogeneously initiated by the stainless steel of the reactor walls. For secondary carbon atoms, high ketone to alcohol ratios are observed (3.5-7.9), most probably due to fast consecutive oxidation of alcoholic intermediates. Since C - C scission reactions are detected only to a very small extent, tertiary carbon atoms are transformed into the corresponding alcohols with high selectivity. Detailed analysis of the product distributions and other mechanistic evidence suggest that acetaldehyde acts not only as the sacrificial oxygen acceptor, but also as an efficient H-atom donor for peroxo and oxo radicals and as a crucial reductant for hydroperoxo intermediates. In comparison to other inert gases such as compressed N, or Ar, the use of carbon dioxide was shown to increase the yields of alkane oxygenates under identical reaction conditions.
- Theyssen, Nils,Hou, Zhenshan,Leitner, Walter
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p. 3401 - 3409
(2008/09/19)
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- Adamantane derivatives and resin compositions using the same as raw material
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The adamantane derivatives of the present invention which are represented by the general formula (1): wherein X is a hydrogen atom, alkyl, halogen-containing alkyl, halogen, or hydroxyl-, halogen-, nitrile- or ether-containing hydrocarbyl, and a plurality of X groups, if any, may be the same or different from each other; n1 is an integer of 1 to 14; R1 to R4 may be the same or different from each other and are independently alkyl or halogen-containing alkyl; and Y1 and Y2 may be the same or different from each other and are independently a hydrogen atom or a group represented by the general formula (2): wherein R5 to R7 may be the same or different from each other and are independently a hydrogen atom, alkyl, halogen or halogen-containing alkyl, are excellent in optical properties, heat resistance and acid-dissociating property, and useful as crosslinking-type resins, optical materials such as optical fibers, light wave guides, optical disk substrates and photoresists as well as raw materials thereof, intermediate products of medicines or agricultural chemicals, and various other industrial products.
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Page/Page column 16-17; 19-20
(2008/06/13)
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- Selective organocatalytic oxygenation of hydrocarbons by dioxygen using anthraquinones and N-hydroxyphthalimide
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(Chemical Equation Presented) Purely organic and catalytic systems of anthraquinones and N-hydroxyphthalimide efficiently promote oxygenation of hydrocarbons with dioxygen under mild conditions, e.g., fluorene can be converted completely to fluorenone with 85% yield at 80°C.
- Yang, Guanyu,Zhang, Qiaohong,Miao, Hong,Tong, Xinli,Xu, Jie
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p. 263 - 266
(2007/10/03)
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- Oxaziridine-mediated catalytic hydroxylation of unactivated 3° C-H bonds using hydrogen peroxide
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The design, structural characterization, and evaluation of a unique class of 1,2,3-benzoxathiazine-based oxaziridines as potent O-atom transfer agents for catalytic C-H hydroxylation and alkene epoxidation are described. Turnover of this reaction is made possible by employing a diaryl diselenide cocatalyst and urea·H2O2 as the terminal oxidant. Oxidation of saturated hydrocarbons is strongly biased toward 3° C-H bonds even in systems possessing a significantly greater number of methylene groups. In addition, the benzoxathiazine catalyst is effective for epoxidation of terminal and electron-deficient olefins. Collectively, these findings represent an important first step toward the advancement of general methodology for selective C-H oxidation. Copyright
- Brodsky, Benjamin H.,Du Bois
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p. 15391 - 15393
(2007/10/03)
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- Liquid-phase epoxidation of alkenes using molecular oxygen catalyzed by vanadium cation-exchanged montmorillonite
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Vanadium cation-exchanged montmorillonite can efficiently catalyze the selective epoxidation of various alkenes and the oxygenation of adamantane using molecular oxygen as a sole oxidant. Copyright
- Mitsudome, Takato,Nosaka, Naoya,Mori, Kohsuke,Mizugaki, Tomoo,Ebitani, Kohki,Kaneda, Kiyotomi
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p. 1626 - 1627
(2007/10/03)
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- METHOD FOR PRODUCING 1,3-ADAMANTANEDIOL
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PROBLEM TO BE SOLVED: To provide a method for inexpensively producing 1,3-adamantanediol important as a raw material for a highly functional material such as a heat-resistant polymer, and an electronic material such as a resist for a semiconductor under a comparatively low pressure of ≤0.4 MPa, preferably ≤0.3 MPa. SOLUTION: The 1,3-adamantanediol is produced by using a 1,3-dihalogenated adamantane, for example, obtained by halogenating adamantane with chlorosulfonic acid as a raw material, and reacting the 1,3-dihalogenated adamantane with water in the presence of a water-soluble organic solvent such as N,N-dimethylformamide, and an alkali or alkaline earth metal salt of a carboxylic acid such as sodium acetate.
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Page/Page column 6
(2008/06/13)
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- MANUFACTURING METHOD OF 1,3-ADAMANTANEDIOL
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PROBLEM TO BE SOLVED: To provide a method for efficiently manufacturing 1,3-adamantanediol which is important as a raw material of highly functional materials such as heat-resistant polymers or of electronic materials such as semiconductor resists or the like under a mild condition. SOLUTION: 1,3-Dichloroadamantane as a raw material, which is obtained, for example, by halogenating adamantane with chlorosulfonic acid, is mixed with sulfuric acid and water and is allowed to react. Thus, 1,3-adamantanediol can be manufactured in a high yield under a mild condition, for example, at 60°C under atmospheric pressure.
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Page/Page column 6
(2008/06/13)
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- Oxidation of adamantane with 1 atm molecular oxygen by vanadium-substituted polyoxometalates
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The oxidation of adamantane with molecular oxygen as a sole oxidant was efficiently promoted by catalyst precursors of vanadium-substituted Keggin-type phosphomolybdates such as H4PVMo11O40, H 5PV2Mo10O40, and H 6PV3Mo9O40 in butyronitrile. The major product was a tertiary CH bond oxygenated product of 1-adamantanol, and secondary CH bond oxygenated products were also formed. The total yield of oxygenated products for the oxidation of adamantane in the presence of H 5PV2Mo10O40 reached 84%. NMR and IR data show that the vanadium-substituted phosphomolybdates, such as H 4PVMo11O40 and H5PV 2Mo10O40, decompose to form the monomeric vanadium species (VVO2+ (main) and VIVO2+) and PMo12O403- Keggin anion. The reaction mechanism involving a radical species was proposed from ESR and kinetic data. The catalysts initially abstract the hydrogen of adamantane to form the adamantyl radical and reduced catalysts. This step would be promoted mainly by the vanadium species, such as VVO2+, and the phosphomolybdates, PMo12O40n-, enhance the activity. The adamantyl radical formed promotes the successive formation of the key intermediates, such as adamantyl radical and hydroperoxide species.
- Shinachi, Satoshi,Matsushita, Mitsunori,Yamaguchi, Kazuya,Mizuno, Noritaka
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- Efficient oxidation of alkane with O2 and H2 by Eu-Ti-Pt catalytic system
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Alkane was efficiently oxidized to alcohol and ketone with O2 and H2 by EuCl3-TiO(acac)2-Pt/SiO2 catalytic system with very high H2-utilization efficiencies, 75% for adamantane and 60% for cyclohexane oxidations. ESR studies suggested that electrons originated in H2 effectively conducted to O2 through Pt, Eu3+/Eu2+, and Ti4+/Ti 3+. Eu2+ and Ti3+ species reductively activated O2, generating active oxygen species. Copyright
- Yamanaka, Ichiro,Gomi, Toshikazu,Nabeta, Takashi,Otsuka, Kiyoshi
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p. 1486 - 1487
(2007/10/03)
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- Method for producing 1,3-adamantanediol
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[PROBREM TO BE SOLVED]: It is a method of important as the raw material that synthesizes various Ada man tongue conductors including the fine polymer, and manufacturing useful 1 and three-Adamantangeorl as various coating materials, and offer the method of efficiently manufacturing a target thing from the reaction under the normal pressure that makes 1 and three-Ge halogenation Ada man tongues a raw material. [SOLUTION]: "1,3-adamantanediols precursor" such as 3-halogenated 1-formyladamantanes etc. is obtained by mixing and reacting 1,3-dihalogenated adamantanes with formic acid, formate salt or metal oxide, then the precursor is mixed and reacted with water to convert to 1,3-adamantanediols.
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Page/Page column 10-11; 13
(2008/06/13)
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- Catalytic oxidation of C-H bonds
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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.
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- Production of adamantanediols
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Adamantanediols are produced by the hydroxylation of adamantane compounds in a water/organic solvent two-phase system in the presence of a ruthenium compound and a hypochlorite. Throughout the hydroxylation, the hypochlorite concentration in the water phase is regulated within a narrow limited range, for example, by monitoring the pH of the reaction system. With such a control of the hypochlorite concentration, the adamantanediols are produced in a high selectivity and a high yield.
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- Chemospecific chromium[VI] catalyzed oxidation of C-H bonds at -40 °C
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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
- Lee, Seongmin,Fuchs
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p. 13978 - 13979
(2007/10/03)
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- Catalyst comprising nitrogen-containing heterocyclic compound, and process for producing organic compound using the catalyst
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A catalyst is for use in a reaction using an oxygen-atom-containing reactant and includes a nitrogen-containing heterocyclic compound of the following formula (1): wherein each of R1and R2is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group, and R1and R2may be combined to form a double bond or to form an aromatic or non-aromatic ring with the adjacent two carbon atoms, where one or two of heterocyclic ring containing three nitrogen atoms indicated in the formula may be further formed on the R1or R2, or on the double bond or aromatic or non-aromatic ring formed by R1and R2; X is an oxygen atom or a hydroxyl group; and Y is a single bond, a methylene group, or a carbonyl group. This catalyst can introduce an oxygen-atom-containing group into an organic substrate under mild conditions.
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