- 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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- Organophotoredox-Mediated Amide Synthesis by Coupling Alcohol and Amine through Aerobic Oxidation of Alcohol
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The combination of an organic photocatalyst [4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6 dicyanobenzene) or 5MeOCzBN (2,3,4,5,6-pentakis(3,6-dimethoxy-9 H-carbazol-9-yl)benzonitrile)], quinuclidine, and tetra-n-butylammonium phosphate (hydrogen-bonding catalyst) was employed for amide bond formations. The hydrogen-bonded OH group activated the adjacent C?H bond of alcohols towards hydrogen atom transfer (HAT) by a radical species. The quinuclidinium radical cation, generated through single-electron oxidation of quinuclidine by the photocatalyst, employed to abstract a hydrogen atom from the α-C?H bond of alcohols selectively due to a polarity effect-produced α-hydroxyalkyl radical, which subsequently converted to the corresponding aldehyde under aerobic conditions. Then the coupling of the aldehyde and an amine formed a hemiaminal intermediate that upon photocatalytic oxidation produced the amide.
- Samanta, Samya,Shah, Sk. Sheriff,Shee, Maniklal,Singh, Amit Kumar,Singh, N. D. Pradeep,Venkatesh, Yarra
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- 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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supporting information
(2019/12/24)
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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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- Synthesis and SAR of 2,3,3a,4-tetrahydro-1H-pyrrolo[3,4-c]isoquinolin- 5(9bH)-ones as 5-HT2C receptor agonists
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A series of 2,3,3a,4-tetrahydro-1H-pyrrolo[3,4-c]isoquinolin-5(9bH)-ones is described, several examples of which exhibit potent 5-HT2C agonism with excellent selectivity over the closely related 5-HT2A and 5-HT2B receptors. Compounds such as 38 and 44 were shown to be effective in reducing food intake in an acute rat feeding model.
- Fevig, John M.,Feng, Jianxin,Rossi, Karen A.,Miller, Keith J.,Wu, Ginger,Hung, Chen-Pin,Ung, Thao,Malmstrom, Sarah E.,Zhang, Ge,Keim, William J.,Cullen, Mary Jane,Rohrbach, Kenneth W.,Qu, Qinling,Gan, Jinping,Pelleymounter, Mary Ann,Robl, Jeffrey A.
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p. 330 - 335
(2013/02/25)
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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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- Directed ortho metalation-based methodology. Halo-, nitroso-, and boro-induced ipso-desilylation. Link to an in situ Suzuki reaction
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(Chemical Equation Presented) Treatment of DoM-derived silylated aromatics 2-4 under standard electrophilic halogenation conditions cleanly affords ipso-desilyation products 5-7, while nitration of methoxy-substituted analogues 8, 9 leads to non-ipso isomers 10, 12 and 11, 13, controlled by a silicon steric effect. Sequential ipso-borodesilylation of 2a, 3a, and 20 followed by treatment with aryl halides under Pd-catalyzed conditions constitutes an in situ Suzuki-Miyaura cross-coupling protocol to biaryls and heterobiaryls 23.
- Zhao, Zhongdong,Snieckus, Victor
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p. 2523 - 2526
(2007/10/03)
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- A direct and mild conversion of tertiary aryl amides to methyl esters using trimethyloxonium tetrafluoroborate: A very useful complement to directed metalation reactions
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The scope and generality of a direct process for the conversion of tertiary amides directly to methyl esters has been investigated. The process involves a two-step, one pot procedure in which a tertiary amide is first treated with trimethyloxonium tetrafluoroborate to generate an imidate intermediate which is then hydrolyzed, generally by the addition of saturated aqueous sodium bicarbonate solution. Although this process fails for aliphatic amides, very good yields are realized for a variety of amides derived from aromatic carboxylic acids. Steric hindrance at the N-alkyl group is well tolerated; thus N,N-dimethyl, -diethyl, and -diisopropyl amides can all be utilized successfully. (C) 2000 Elsevier Science Ltd.
- Keck, Gary E,McLaws, Mark D,Wager, Travis T
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p. 9875 - 9883
(2007/10/03)
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- Fungicides for the control of take-all disease of plants
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A method of controlling Take-All disease of plants by applying a fungicide of the formula STR1 wherein Z1 and Z2 are C and are part of an aromatic ring which is benzothiophene; and A is selected from --C(X)-amine wherein the amine is an unsubstituted, monosubstituted or disubstituted amino radical, --C(O)--SR3, --NH--C(X)R4, and --C(=NR3)--XR7 ; B is --Wm --Q(R2)3 or selected from O-tolyl, 1-naphthyl, 2-naphthyl, and 9-phenanthryl, each optionally substituted with halogen or R4 ; Q is C, Si, Ge, or Sn; W is --C(R3)p H(2-p) --; or when Q is C, W is selected from --C(R3)p H(2-p), --N(R3)m H(1-m)--, --S(O)p--, and --O--; X is 0 or S; n is 0, 1, 2, or 3; m is 0 or 1; p is 0, 1, or 2; each R and R2 is independently defined herein; R3 is C1 -C4 alkyl; R4 is C1 -C4 alkyl, haloalkyl, alkoxy, alkylthio, alkylamino, or dialkylamino; and R7 is C1 -C4 alkyl, haloalkyl, or phenyl, optionally substituted with halo, nitro, or R4 ; or an agronomic salt thereof.
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- o-CHLOROTHIOBENZAMIDES AS ADDITIVES TO LUBRICATING OILS.
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The authors report the results of synthesis of o-chlorothiobenzamides and of a study of their properties as lubricant additives. The results of tests of the anticorrosion properties of o-chlorothiobenzamides were compared with the results of tests on compounds of analogous structure: thiobenzamides and o-chlorobenzamides. The results show that o-chlorothiobenzamides added to DS-11 oil have definite anticorrosion and antiwear effects, manifested in decrease of the degree of corrosion and of the diameter of the wear patch (D//p).
- Kuliev,Kurbanov,Mamedov,Kuliev
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p. 139 - 142
(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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