- Stepwise benzylic oxygenation via uranyl-photocatalysis
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Stepwise oxygenation at the benzylic position (1°, 2°, 3°) of aromatic molecules was comprehensively established under ambient conditions via uranyl photocatalysis to produce carboxylic acids, ketones, and alcohols, respectively. The accuracy of the stepwise oxygenation was ensured by the tunability of catalytic activity in uranyl photocatalysis, which was adjusted by solvents and additives demonstrated through Stern–Volmer analysis. Hydrogen atom transfer between the benzylic position and the uranyl catalyst facilitated oxygenation, further confirmed by kinetic studies. Considerably improved efficiency of flow operation demonstrated the potential for industrial synthetic application.
- Hu, Deqing,Jiang, Xuefeng
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supporting information
p. 124 - 129
(2022/01/19)
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- Catalytic Aerobic Oxidation of Alkenes with Ferric Boroperoxo Porphyrin Complex; Reduction of Oxygen by Iron Porphyrin
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We herein describe the development of a mild and selective catalytic aerobic oxidation process of olefins. This catalytic aerobic oxidation reaction was designed based on experimental and spectroscopic evidence assessing the reduction of atmospheric oxygen using a ferric porphyrin complex and pinacolborane to form a ferric boroperoxo porphyrin complex as an oxidizing species. The ferric boroperoxo porphyrin complex can be utilized as an in-situ generated intermediate in the catalytic aerobic oxidation of alkenes under ambient conditions to form oxidation products that differ from those obtained using previously reported ferric porphyrin catalysis. Moreover, the mild reaction conditions allow chemoselective oxidation to be achieved.
- Kimura, Kento,Kurahashi, Takuya,Matsubara, Seijiro,Murano, Shunpei
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supporting information
p. 2493 - 2497
(2021/12/29)
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- Late-Stage Intermolecular Allylic C-H Amination
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Allylic amination enables late-stage functionalization of natural products where allylic C-H bonds are abundant and introduction of nitrogen may alter biological profiles. Despite advances, intermolecular allylic amination remains a challenging problem due to reactivity and selectivity issues that often mandate excess substrate, furnish product mixtures, and render important classes of olefins (for example, functionalized cyclic) not viable substrates. Here we report that a sustainable manganese perchlorophthalocyanine catalyst, [MnIII(ClPc)], achieves selective, preparative intermolecular allylic C-H amination of 32 cyclic and linear compounds, including ones housing basic amines and competing sites for allylic, ethereal, and benzylic amination. Mechanistic studies support that the high selectivity of [MnIII(ClPc)] may be attributed to its electrophilic, bulky nature and stepwise amination mechanism. Late-stage amination is demonstrated on five distinct classes of natural products, generally with >20:1 site-, regio-, and diastereoselectivity.
- Clark, Joseph R.,Dixon, Charlie F.,Feng, Kaibo,Han, Wei,Ide, Takafumi,Koch, Vanessa,Teng, Dawei,Wendell, Chloe I.,White, M. Christina
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supporting information
p. 14969 - 14975
(2021/10/01)
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- Novel synthesis method of ester compound
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The invention discloses a synthesis method of an ester compound. The method comprises the following steps: carrying out an oxa-Michael addition reaction by using organic carboxylic acid and alpha,beta-unsaturated ketone as initial raw materials and a sodi
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Paragraph 0011-0012
(2020/06/09)
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- Regioselective Wacker-Type Oxidation of Internal Olefins in tBuOH Using Oxygen as the Sole Oxidant and tBuONO as the Organic Redox Cocatalyst
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A regioselective Wacker-Tsuji oxidation of internal olefins in tBuOH has been developed using oxygen as the terminal oxidant and tert-butyl nitrite as the simple organic redox cocatalyst without the involvement of hazardous cocatalysts or harsh reaction conditions. A series of internal olefins bearing various functional groups can be oxidized to the corresponding substituted ketones in generally good yields with high regioselectivities.
- Huang, Qing,Li, Ya-Wei,Ning, Xiao-Shan,Jiang, Guo-Qing,Zhang, Xiao-Wei,Qu, Jian-Ping,Kang, Yan-Biao
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p. 965 - 969
(2020/02/15)
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- Isopropenyl acetate: A cheap and general acylating agent of alcohols under metal-free conditions
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Functionalized primary, secondary and tertiary alcohols are efficiently acetylated by isopropenyl acetate and catalytic p-TsOH.
- Temperini, Andrea,Minuti, Lucio,Morini, Tommaso,Rosati, Ornelio,Piazzolla, Francesca
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p. 4051 - 4053
(2017/09/27)
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- Transition-metal free alkylarylation of acrylamides initiated by radical C-C bond cleavage of the tertiary cycloalkanols
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An efficient Na2S2O8-promoted radical cyclization reaction of acrylamides with the tertiary cycloalkanols has been developed. This one pot procedure involves a tandem C-C bond cleavage and two C-C bonds formation process.
- Guo, Li-Na,Deng, Zhi-Qiang,Wu, Yong,Hu, Jie
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p. 27000 - 27003
(2016/03/25)
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- Selective oxidation of alcohols with alkali metal bromides as bromide catalysts: Experimental study of the reaction mechanism
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A bromide-catalyzed oxidation of alcohols was developed which proceeded in the presence of an alkali metal bromide and an oxidant under mild conditions. The reaction involved an organic-molecule-free oxidation using KBr and Oxone and a Br?nsted acid assisted oxidation using KBr and aqueous H 2O2 solution to provide a broad range of carbonyl compounds in high yields. Moreover, the bromide-catalyzed oxidation of primary alcohols enabled the divergent synthesis of carboxylic acids and aldehydes under both reaction conditions in the presence of TEMPO. A possible catalytic mechanism was suggested on the basis of various mechanistic studies.
- Moriyama, Katsuhiko,Takemura, Misato,Togo, Hideo
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p. 6094 - 6104
(2014/07/21)
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- PROCESS FOR THE SYNTHESIS OF KETONES FROM INTERNAL ALKENES
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The present invention is directed to methods for oxidizing internal olefins to ketones. In various embodiments, each method comprising contacting an organic substrate, having an initial internal olefin, with a mixture of (a) a biscationic palladium salt; and (b) an oxidizing agent; dissolved or dispersed in a solvent system to form a reaction mixture, said solvent system comprising at least one C2-6 carbon nitrile and optionally at least one secondary alkyl amide, said method conducted under conditions sufficient to convert at least 50 mol % of the initial internal olefin to a ketone, said ketone positioned on a carbon of the initial internal olefin. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed oil derivatives and a bioactive natural product are described.
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Paragraph 0122; 0131; 0149
(2014/07/22)
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- Practical and general palladium-catalyzed synthesis of ketones from internal olefins
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Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features. Copyright
- Morandi, Bill,Wickens, Zachary K.,Grubbs, Robert H.
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supporting information
p. 2944 - 2948
(2013/04/10)
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- Direct and selective benzylic oxidation of alkylarenes via C-H abstraction using alkali metal bromides
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A direct benzylic oxidation of alkylarenes via C-H bond abstraction was developed using alkali metal bromides and oxidants under mild conditions. This reaction proceeded with excellent selectivity by thermal oxidation or photooxidation to provide a broad range of carbonyl compounds containing electron-deficient aryl carbonyl compounds in high yields.
- Moriyama, Katsuhiko,Takemura, Misato,Togo, Hideo
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supporting information; experimental part
p. 2414 - 2417
(2012/06/18)
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- A novel, green 1-glycyl-3-methyl imidazolium chloride-copper(II) complex catalyzed CH oxidation of alkyl benzene and cyclohexane
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A variety of alkyl-arenes and cyclohexane were converted to the corresponding ketones with NaClO as the oxidant in the presence of 1-glycyl-3-methyl imidazolium chloride-copper(II) complex. This method contains simplified product isolation and catalyst recycling, affording benzylic CH oxidation of alkyl-arenes imparting high yield of ketones. Furthermore, complex could be reused seven times without a significant loss of its catalytic activity.
- Karthikeyan, Parasuraman,Bhagat, Pundlik Rambhau,Kumar, S. Senthil
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scheme or table
p. 681 - 684
(2012/08/07)
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- New heteroannulation reactions of N-Alkoxybenzamides by Pd(II) Catalyzed C-H activation
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A new palladium(II) catalyzed methodology for the direct synthesis of alkylidene isoindolinones from N-alkoxybenzamides is presented. Isoindolinone formation proceeds through a highly efficient and E-selective C-H activation/Heck/Aza-Wacker sequence. Subs
- Wrigglesworth, Joe W.,Cox, Brian,Lloyd-Jones, Guy C.,Booker-Milburn, Kevin I.
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supporting information; experimental part
p. 5326 - 5329
(2011/12/01)
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- DERIVATIVES OF 4-(2-AMINO-1-HYDROXYETHYL)PHENOL AS AGONISTS OF THE β2 ADRENERGIC RECEPTOR
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The present invention provides a Compound of formula (I), wherein: R1 is a group selected from -CH2OH,-NH(CO)H; and R2 is a hydrogen atom; or R1 together with R2 form the group -NH-C(O)-CH=CH-, wherei
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Page/Page column 67-68
(2008/12/05)
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- A simple synthetic protocol for oxidation of alkyl-arenes into ketones using a combination of HBr-H2O2
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A wide variety of alkyl- and cycloalkyl-arenes undergo benzylic C-H oxidation by employing a combination of 48% hydrogen bromide and 30% hydrogen peroxide in dichloromethane at room temperature. In addition, a chemoselective oxidation at the benzylic position is feasible by deactivating the aromatic ring using the same combination.
- Khan, Abu T.,Parvin, Tasneem,Choudhury, Lokman H.,Ghosh, Subrata
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p. 2271 - 2274
(2007/10/03)
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- DERIVATIVES OF 4-(2-AMINO-1-HYDROXYETHYL)PHENOL AS AGONISTS OF THE β2 ADRENERGIC RECEPTOR
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The present invention provides a compound of formula (I) wherein: R1 is a group selected from -CH2OH, -NHC(O)H and R2 is a hydrogen atom; or R1 together with R2 form the group -NH-C(O)-CH=CH- wherein the nitrogen atom is bound to the carbon atom in the phenyl ring holding R1 and the carbon atom is bound to the carbon atom in the phenyl ring holding R2; R3 is selected from hydrogen and halogen atoms or groups selected from -SO-R5, -SO2- R5, -NH-CO-NH2, -CO-NH2, hydantoino, C1-4alkyl, C1-4alkoxy and -SO2NR5R6; R4 is selected from hydrogen atoms, halogen atoms and C1-4alkyl groups; R5 is a C1-4alkyl group or C3-8 cycloalkyl; R6 is independently selected from hydrogen atoms and C1-4alkyl groups; n, p and q are independently 0, 1 , 2, 3 or 4; m and s are independently 0, 1 , 2 or 3; r is 0, 1 or 2; with the provisos that: at least one of m and r is not 0; the sum n+m+p+q+r+s is 7, 8, 9, 10, 11 , 12 or 13; the sum q+r+s is 2, 3, 4, 5 or 6 or a pharmaceutically-acceptable salt, solvate or stereoisomer thereof.
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Page/Page column 71
(2008/06/13)
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- Direct conversion of bromohydrins to ketones by a free radical elimination of hydrogen bromide
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Secondary β-bromo alcohols can be transformed directly to ketones in very good yields by a free radical process. Tertiary β-bromo alcohols do not react while the primary ones are transformed to aldehydes in lower yields. The reaction involves an abstraction of a hydrogen atom α to an OH group, followed by elimination of the bromine atom and subsequent tautomerization of an enol to a ketone.
- Dolenc, Darko,Harej, Maja
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p. 312 - 313
(2007/10/03)
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- METHOXYMETHYL METHYL SULFATE - A NEW REAGENT FOR THE FUNCTIONALIZATION OF OLEFINS AND ACETYLENES
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The reaction of methylenecyclobutane, styrene, 1-hexene, and phenyl- and diphenylacetylenes with methoxymethyl methyl sulfate, generated in situ from methylal and sulfur trioxide, takes place as conjugate addition of the methoxymethyl and methyl sulfate groups and leads to the respective alkoxymethyl sulfates in the case of olefins and vinyl methyl sulfates in the case of acetylenes.The high reactivity of the obtained compounds in reactions with nucleophiles was used for the synthesis of diethers, unsaturated ethers, and acetoxy and α,β-unsaturated ketones.
- Lebedev, M. Yu.,Balenkova, E. S.
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p. 1214 - 1219
(2007/10/02)
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- Palladium(II)-catalyzed Alkoxylation and Acetoxylation of Alkenes
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Addition of alcohols or acetic acid to alkenes activated by carbonyl or acetal is catalyzed by PdCl2(MeCN)2 to give the corresponding ethers and esters.
- Hosokawa, Takahiro,Shinohara, Toru,Ooka, Yoshiharu,Murahashi, Shun-Ichi
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p. 2001 - 2004
(2007/10/02)
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