- METHOD FOR PRODUCING KETONE DERIVATIVE
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PROBLEM TO BE SOLVED: To provide a method for producing a ketone derivative using a zinc derivative with high stability. SOLUTION: For example, a toluene solution of 6-decanethio-6-oxo hexanoic acid methyl and a 10% Pd/C-DMF suspension are added into a THF solution of phenyl pivalic acid zinc sequentially for a reaction, to synthesize 5-benzoylpentanoic acid methyl on the right side in the formula shown below. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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- Metal-Free, Visible-Light-Induced Selective C?C Bond Cleavage of Cycloalkanones with Molecular Oxygen
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A metal-free, visible-light-induced oxidative C?C bond cleavage of cycloketones with molecular oxygen is described. Cooperative Br?nsted-acid catalysis and photocatalysis enabled selective C?C bond cleavage of cycloketones to generate an array of γ-, δ- and ?-keto esters under very mild conditions. Mechanistic studies indicate that singlet molecular oxygen (1O2) is responsible for this transformation.
- Xin, Hong,Duan, Xin-Hua,Liu, Le,Guo, Li-Na
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supporting information
p. 11690 - 11694
(2020/08/21)
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- Ni-Catalyzed β-Alkylation of Cyclopropanol-Derived Homoenolates
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Metal homoenolates are valuable synthetic intermediates which provide access to β-functionalized ketones. In this report, we disclose a Ni-catalyzed β-alkylation reaction of cyclopropanol-derived homoenolates using redox-active N-hydroxyphthalimide (NHPI) esters as the alkylating reagents. The reaction is compatible with 1°, 2°, and 3° NHPI esters. Mechanistic studies imply radical activation of the NHPI ester and 2e β-carbon elimination occurring on the cyclopropanol.
- Mills, L. Reginald,Zhou, Cuihan,Fung, Emily,Rousseaux, Sophie A. L.
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p. 8805 - 8809
(2019/11/03)
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- Oxygenation of Simple Olefins through Selective Allylic C?C Bond Cleavage: A Direct Approach to Cinnamyl Aldehydes
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A novel metal-free allylic C?C σ-bond cleavage of simple olefins to give valuable cinnamyl aldehydes is reported. 1,2-Aryl or alkyl migration through allylic C?C bond cleavage occurs in this transformation, which is assisted by an alkyl azide reagent. This method enables O-atom incorporation into simple unfunctionalized olefins to construct cinnamyl aldehydes. The reaction features simple hydrocarbon substrates, metal-free conditions, and high regio- and stereoselectivity.
- Liu, Jianzhong,Wen, Xiaojin,Qin, Chong,Li, Xinyao,Luo, Xiao,Sun, Ao,Zhu, Bencong,Song, Song,Jiao, Ning
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supporting information
p. 11940 - 11944
(2017/09/20)
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- Effect of carbon chain length in the substituent of PCBM-like molecules on their photovoltaic properties
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A series of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM)-like fullerene derivatives with the butyl chain in PCBM changing from 3 to 7 carbon atoms, respectively (F1-F5), are designed and synthesized to investigate the relationship between
- Zhao, Guangjin,He, Youjun,Xu, Zheng,Hou, Jianhui,Zhang, Maojie,Min, Jie,Chen, Hsiang-Yu,Ye, Mingfu,Hong, Ziruo,Yang,Li, Yongfang
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experimental part
p. 1480 - 1487
(2011/12/02)
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- One-pot synthesis of oxo acid derivatives by RhI-catalyzed chelation-assisted hydroacylation
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Various oxo acid derivatives were obtained directly from the reaction of aliphatic and aromatic aldehydes with ω-alkenoic acid derivatives in the presence of rhodium(I) complexes and 2-amino-3-picoline. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Jo, Eun-Ae,Jun, Chul-Ho
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p. 2504 - 2507
(2007/10/03)
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- Polymer-supported tertiary amine in organic synthesis: A useful reagent in the conversion of alkenes to carbonyl compounds via the corresponding ozonides
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Polymer-supported tertiary amine 6 is useful to workup the ozonolytic reaction of alkenes. The corresponding carbonyl products can be isolated in excellent yields by simple filtration. For some substituted alkenes, carboxylic acids were formed as the major products and can be isolated from the polymeric resin by washing with 1M HCl followed by extraction with organic solvent. In all cases, simply washing with aqueous NaOH can regenerate the polymeric amine 6. The reactivity of the regenerated polymeric amine is as effective as that of the freshly prepared one.
- Hon, Yung-Son,Wu, Kun-Chan
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p. 493 - 498
(2007/10/03)
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- Oxidation of 2-alkylcycloalkanones with iodine-cerium(IV) salts in alcohols
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The reaction of 2-alkylcycloalkanones with iodine-cerium(IV) salts in alcohols (methanol, ethanol, propan-1-ol or propan-2-ol) gave the respective oxo ester in 28-98% yields.
- He, Liangyou,Kanamori, Miyuki,Horiuchi, C. Akira
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p. 122 - 123
(2007/10/03)
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- Oxidation of 2-substituted cycloalkanones with cerium(IV) sulfate tetrahydrate in alcohols and acetic acid
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The reaction of 2-substituted cycloalkanones with cerium(IV) sulfate tetrahydrate (CS) in alcohols and acetic acid gave the corresponding alkyl esters of oxo acids (80-96%) and oxo acids (78-96%), respectively, by oxidative cleavage of the C(R).C=O bond. In the case of 2-iodocycloalkanones in methanol, the dimethyl ester was obtained in good yield. A treatment of 5α-cholestan-3-one with CS in methanol produced 2-acetal 3-ester of 2,3-seco derivative in good yield. The effects of cerium(IV) and copper(II) salts are also discussed.
- He, Liangyou,Horiuchi, C. Akira
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p. 2515 - 2521
(2007/10/03)
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- Generation of β-Carbonyl Radicals from Cyclopropanol Derivatives by the Oxidation with Manganese(III) 2-Pyridinecarboxylate and Their Reactions with Electron-Rich and -Deficient Olefins
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Various β-carbonyl radicals are generated oxidatively from cyclopropanol derivatives by the use of manganese(III) 2-pyridinecarboxylate (Mn(pic)3).These β-carbonyl radicals react with electron-rich olefins such as conjugated silyl enol ethers, a ketene th
- Iwasawa, Nobuharu,Hayakawa, Satoshi,Funahashi, Masahiro,Isobe, Koichi,Narasaka, Koichi
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p. 819 - 827
(2007/10/02)
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- Orientation of the benzophenone group at various depths in bilayers
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The hydrophobic core of biological membranes is primarily composed of fatty acyl chains of lipids and side chains of nonpolar amino acids belonging to membrane-spanning domains of transmembrane proteins. Electron transport across the 35-40-? membrane dielectric takes place via suitably oriented electron-transfer groups associated with transmembrane domains of membrane-bound proteins. We propose here that the design of lipids bearing electron-transport groups oriented at different depths can provide the necessary supramolecular assembly in the form of a monolayer or a bilayer to carry out electron transfer. The design of these modified lipids is crucial to the success of such a molecular device. We report here the design and synthesis of three benzophenone-based phospholipids capable of orienting the benzophenone group at different depths in a bilayer. The orientation of the benzophenone group was determined by photochemical cross-linking of these lipids with dimyristoylphosphatidylcholine in single bilayer vesicles followed by mass spectral analyses of the cross-linked products. The actual site of cross-linking on the myristoyl chain was determined, and it was observed that a range of carbon atoms are functionalized. The range of carbon atoms functionalized was found to be centered around the position expected from the transverse location of the benzophenone-based phospholipid in the bilayer. The data could be best interpreted in terms of zones of carbon atoms functionalized rather than any discreet site. This is in keeping with the current models of membranes which suggest the presence of a fluid gradient as one goes down the fatty acyl chain in the membrane. However, the range of carbon atoms functionalized was narrowed with probes reported here. The use of a hydrophobic tail attached to the benzophenone group assisted in directing the orientation of the photoactive group at different depths. Besides providing an effective design strategy for the orientation of electron-transfer groups at different depths in a bilayer, the high insertion yield and the depth-dependent labeling observed in artificial membranes suggest that the benzophenone-based phospholipids reported here could also prove useful for studying the structure of single and multiple spanning transmembrane proteins.
- Lala, Anil K.,Ravi Kumar
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p. 3982 - 3988
(2007/10/02)
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- Nonacarbonyldiiron-, Pentacarbonyliron-, or Hexacarbonylmolybdenum-induced Reactions of 4,5-Polymethylene-substituted 2-Isoxazolines
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The reaction of 4,5-polymethylene-substituted 2-isoxazolines, 3-phenyl-3a,5,6,7a-tetrahydro-4H-pyranoisoxazole or 3-phenyl-3a,4,5,6a-tetrahydrofuroisoxazole, with , , or resulted in the formation of 5-hydroxy-1-phenyl-1-pentanone or 4-hydroxy-1-phenyl-1-butanone, via the N-O and C-C bond cleavage of the 2-isoxazoline ring and the subsequent hydrolysis.The similar reaction of 7a-morpholino- and 7a-(1-pyrrolidinyl)-3-phenyl-3a,4,5,6,7,7a-hexahydro-1,2-benzoisoxazoles undergoes the N-O bond cleavage and, the subsequent elimination of the amino group or the C-3a-C-7a bond fission.Although the reaction of 6a-morpholino- and 6a-(1-pyrrolidinyl)-3-phenyl-3a,4,5,6a-tetrahydro-4H-cyclopentisoxazoles with undergoes the N-O bond cleavage, and the subsequent elimination of the amino group or the C-3a-C-6a bond fission, the reaction of those 2-isoxazolines with proceeds very slowly.The mechanisms are proposed for these reactions.
- Nitta, Makoto,Yi, Akihiro,Kobayashi, Tomoshige
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p. 991 - 994
(2007/10/02)
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- Aspects of Tautomerism. 13. Alkaline Hydrolysis of γ-, δ-, and ε-Keto Esters and their Desoxy Analogues. Geometrical Constraints on Keto Participation
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The rates of alkaline hydrolysis of methyl β-benzoylpropionate (I), methyl γ-benzoylbutyrate (II) and methyl δ-benzoylvalerate (III) decrease in the order I>II>III.Keto participation is the predominant pathway in the case of γ-keto esters.Evidence has also been obtained for keto participation in the case of δ-keto esters, whereas no such evidence is available in the case of ε-keto esters studied.
- Bhatt, M. Vivekananda,Ravindranathan, M.,Somayaji, Viswanatha,Rao, G. Venkoba
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p. 3170 - 3173
(2007/10/02)
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- Aspects of Tautomerism: Part X - Neighbouring Group Effects on the Structure and Reactivity Patterns of Acid Chlorides
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The influence of neighbouring groups on the structure and reactivity patterns of over one hundred acid chlorides derived from γ- and δ-keto acids, 1,2- and 1,3-dicarboxylic acid half-esters and diacid chlorides have been examined.Contrary to reports in the literature, text books and monographs, evidence has been obtained for the non-existence of tautomerism between the isomeric pairs of either acid chlorides or half-ester acid chlorides.ce.
- Bhatt, M. Vivekananda,El Ashry, Shaker H.,Somayaji, Vishwanatha
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p. 473 - 486
(2007/10/02)
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