- Visible light-driven photocatalytic duet reaction catalyzed by the B12-rhodium-titanium oxide hybrid catalyst
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The hybrid catalyst composed of the B12 complex and rhodium ion (Rh3+) modified titanium oxide was synthesized for the visible light-driven B12 inspired catalytic reaction. The hybrid catalyst contains 4.93 × 10?6 molg?1 of the B12 complex and 5.43 × 10?5 molg?1 of the Rh(III) ion on the surface of titanium oxide. Visible light irradiation (λ ≧ 420 nm) of the hybrid catalyst in the presence of triethylamine (Et3N) as a sacrificial reagent showed absorption at 390 nm, typical for the Co(I) state of the B12 complex monitored by diffuse reflectance UV–vis analysis, which imply that electron transfer from the titanium oxide to Co(III) center of the B12 complex occurred by the visible light irradiation. Benzotrichloride was converted to N,N-diethylbenzamide by the visible light irradiation catalyzed by the hybrid catalyst in air at room temperature. Both the conduction band electron and valence band hole of the catalyst were utilized for the reaction to form the amide product. The reaction mechanism of the duet reaction was proposed.
- Shichijo, Keita,Fujitsuka, Mamoru,Hisaeda, Yoshio,Shimakoshi, Hisashi
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- Investigations on N,N-Dialkylbenzamides by NMR Spectroscopy. 5 - Analysis of Static and Dynamic Proton NMR Spectra of 2-Fluoro- and 2,6-Difluoro-N,N-dimethyl- and N,N-Diethyl-benzamides
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The analysis of static and dynamic proton NMR spectra of 2-fluoro- and 2,6-difluoro-N,N-dimethyl- and N,N-diethyl-benzamides at various temperatures has been carried out.The conformations of the compounds have been deduced on the basis of long-range through-space proton-fluorine couplings.Free energies of activation of amide rotation have been determined for all compounds, and of carbonyl-ring rotation for one compound.
- Duerst, Thomas,Gryff-Keller, Adam,Terpinski, Jacek
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- One-Pot Synthesis of Tertiary Amides from Organic Trichlorides through Oxygen Atom Incorporation from Air by Convergent Paired Electrolysis
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A convergent paired electrolysis catalyzed by a B12 complex for the one-pot synthesis of a tertiary amide from organic trichlorides (R-CCl3) has been developed. Various readily available organic trichlorides, such as benzotrichloride and its derivatives, chloroform, dichlorodiphenyltrichloroethane (DDT), trichloro-2,2,2-trifluoroethane (CFC-113a), and trichloroacetonitrile (CNCCl3), were converted to amides in the presence of tertiary amines through oxygen incorporation from air at room temperature. The amide formation mechanism in the paired electrolysis, which was mediated by a cobalt complex, was proposed.
- Luo, Zhongli,Imamura, Kenji,Shiota, Yoshihito,Yoshizawa, Kazunari,Hisaeda, Yoshio,Shimakoshi, Hisashi
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p. 5983 - 5990
(2021/05/04)
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- Palladium-Catalyzed N-Acylation of Tertiary Amines by Carboxylic Acids: A Method for the Synthesis of Amides
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A palladium-catalyzed N-acylation of tertiary amines by carboxylic acids was achieved through C-N cleavage. This reaction showed a wide substrate scope. Both aromatic and aliphatic acids served well as the acylating reagents and coupled with tertiary amines to produce the corresponding amides in good to excellent yields. With the strategy, bioactive carboxylic acids were also efficiently modified, highlighting the synthetic value of the process in organic synthesis.
- Li, Zhaohui,Liu, Long,Xu, Kaiqiang,Huang, Tianzeng,Li, Xinyi,Song, Bin,Chen, Tieqiao
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supporting information
p. 5517 - 5521
(2020/07/14)
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- Visible Light-Driven, One-pot Amide Synthesis Catalyzed by the B12 Model Complex under Aerobic Conditions
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A visible light responsive catalytic system with the B12 complex as the catalyst and [Ir(dtbbpy)(ppy)2]PF6 as the photosensitizer was developed. It provides a convenient and efficient way to synthesize amides. Based on this method, trichlorinated organic compounds were converted into amides in the presence of an amine under aerobic conditions at room temperature in a one-pot procedure. Various trichlorinated organic compounds and an amine source, such as primary, secondary, and cyclic amines, have been evaluated for this transformation, providing the expected products in moderate to excellent yields. Notably, product formation depended on the reaction atmosphere where the amide was obtained under aerobic conditions while partially dechlorinated products were obtained under anaerobic conditions. As this protocol is free from hazardous reagents, extra additives, noble metals, and dangerous gas, the present method provides a novel and efficient approach for amide synthesis under mild and easily controlled conditions.
- Tian, Hui,Shimakoshi, Hisashi,Ono, Toshikazu,Hisaeda, Yoshio
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p. 237 - 240
(2018/12/13)
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- Nitrate-promoted Selective C-H Fluorination of Benzamides and Benzeneacetamides
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A versatile and site-selective nitrate-promoted C-H bond fluorination using various weak coordinating amides as intrinsic directing groups was developed. Diverse tertiary and secondary amides underwent selective aromatic C-H bond fluorination, which featu
- Ning, Xing-Qian,Lou, Shao-Jie,Mao, Yang-Jie,Xu, Zhen-Yuan,Xu, Dan-Qian
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supporting information
p. 2445 - 2448
(2018/04/27)
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- A practical in situ generation of the schwartz reagent. reduction of tertiary amides to aldehydes and hydrozirconation
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A new, highly efficient in situ protocol (Cp2ZrCl2/LiAlH(OBu-t)3) is described for the generation of the Schwartz reagent which provides a convenient method for the amide to aldehyde reduction and the regioselective hydrozirconation-iodination of alkynes and alkenes. Highlighted are chemoselective reductions of benzamides derived by directed ortho metalation (DoM) chemistry, allowing the synthesis of valuable 1,2,3-substituted benzaldehydes. The single-step, three-component process proceeds in a very short reaction time, shows excellent functional group compatibility, and uses inexpensive and long-storage stable reducing reagents.
- Zhao, Yigang,Snieckus, Victor
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p. 390 - 393
(2014/04/03)
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- Discovery of (R)-9-ethyl-1,3,4,10b-tetrahydro-7-trifluoromethylpyrazino[2, 1-a]isoindol-6(2H)-one, a selective, orally active agonist of the 5-HT 2C receptor
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Robust pharmaceutical treatment of obesity has been limited by the undesirable side-effect profile of currently marketed therapies. This paper describes the synthesis and optimization of a new class of pyrazinoisoindolone- containing, selective 5-HT2C agonists as antiobesity agents. Key to optimization of the pyrazinoisoindolone core was the identification of the appropriate substitution pattern and functional groups which led to the discovery of (R)-9-ethyl-1,3,4,10b-tetrahydro-7-trifluoromethylpyrazino[2,1-a] isoindol-6(2H)-one (58), a 5-HT2C agonist with > 300-fold functional selectivity over 5-HT2B and > 70-fold functional selectivity over 5-HT2A. Oral dosing of 58 reduced food intake in an acute rat feeding model, which could be completely reversed by a selective 5-HT2C antagonist and caused a reduction in body weight gain in a 4-day rat model.
- Wacker, Dean A.,Varnes, Jeffrey G.,Malmstrom, Sarah E.,Cao, Xueying,Hung, Chen-Pin,Ung, Thao,Wu, Ginger,Zhang, Ge,Zuvich, Eva,Thomas, Michael A.,Keim, William J.,Cullen, Mary Jane,Rohrbach, Kenneth W.,Qu, Qinling,Narayanan, Rangaraj,Rossi, Karen,Janovitz, Evan,Lehman-McKeeman, Lois,Malley, Mary F.,Devenny, James,Pelleymounter, Mary Ann,Miller, Keith J.,Robl, Jeffrey A.
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p. 1365 - 1379
(2007/10/03)
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- Process for selectively ortho-fluorinating substituted aromatic compounds
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The invention describes a process for selectively preparing ortho-fluorinated substituted aromatic compounds wherein an aromatic compound containing a substituent capable of directing ortho metalation is contacted with a metalating reagent under reaction conditions sufficient to form an ortho-metalated substituted aromatic compound. The ortho-metalated substituted aromatic compound is reacted with an electrophilic fluorinating reagent under reaction conditions sufficient to form the desired ortho-fluorinated substituted aromatic compound which is then recovered from the reaction mixture. The process which utilizes a metalation intermediate prior to effecting the electrophilic fluorination step overcomes problems associated with prior art electrophilic fluorination processes which do not proceed through a regiospecifically controlled intermediate.
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- Directed ortho metalation of n,n-diethyl benzamides. Methodology and regiospecific synthesis of useful contiguously tri- and tetra-substituted oxygenated aromatics, phthalides and phthalic anhydrides
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Full experimental details for the directed ortho metalation approch to a variety of simple ortho-substituted N,N-diethyl benzamides (Table 1) and contiguously 1,2,3- and 1,2,3,4-substituted benzamides (Tables 2) are given. The efficient conversion of these benzamides (6, 10, 12, 13, 18, 19) into phthalides (9a-b, 16b-c, 17) and phthalic anhydrides (8,16a), compounds previously available by demanding, classical methods, is detailed. A short synthesis of iso-ochracinic acid (27) is described.
- De Silva,Reed,Billedeau,Wang,Norris,Snieckus
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p. 4863 - 4878
(2007/10/02)
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- INVESTIGATIONS ON N,N-DIALKYLBENZAMIDES BY NMR SPECTROSCOPY. PART IV. COMPARISON OF BARRIERS TO ROTATION ABOUT THE AMINE C-N BOND IN ORTHO-SUBSTITUTED N,N-DIMETHYL-AND N,N-DIETHYLBENZAMIDES
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The barriers to rotation about the amide C-N bond in a series of ortho-substituted N,N-dimethyl and N,N-diethylbenzamides have been compared.It has been stated that for most of substituents, namely CH3, Cl, Br, I and NO2, the rates of rotation in both series of compounds are identical within the accuracy of measurement (kEt/kMe ca.1).The remaining compounds (F, CN, CH3) show a higher rate of rotation in the series of diethylbenzamides (kEt/kMe ca.1,5).An exception are the OH derivatives in which the internal H-bond is present and because of that the barrier to rotation is lowered and the kEt/kMe ratio raised up to 2.3.
- Gryf-Keller, Adam,Terpinski, Jacek,Zajaczkowska-Terpinska, Ewa
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p. 429 - 434
(2007/10/02)
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