- Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines
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Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.
- Yi, Jaeeun,Kim, Hyun Tae,Jaladi, Ashok Kumar,An, Duk Keun
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supporting information
p. 129 - 132
(2021/11/17)
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- Palladium-Catalyzed Aminocarbonylation of Aryl Halides with N,N-Dialkylformamide Acetals
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We developed a protocol for the palladium-catalyzed aminocarbonylation of aryl halides using less-toxic formamide acetals as bench-stable aminocarbonyl sources under neutral conditions. Various aryl (including heteroaryl) halides reacted with N,N-dialkylformamide acetals in the presence of a catalytic amount of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct and xantphos to give the corresponding aromatic carboxamides at 90–140 °C without any activating agents or bases in up to quantitative chemical yield. This protocol was applied to aryl bromides, aryl iodides, and trifluoromethanesulfonic acid, as well as to relatively less-reactive aryl chlorides. A wide range of functionalities on the aromatic ring of the substrates were tolerated under the aminocarbonylation conditions. The catalytic aminocarbonylation was used to prepare the insect repellent N,N-diethyl-3-methylbenzamide as well as a synthetic intermediate of the dihydrofolate reductase inhibitor triazinate.
- Hirata, Shuichi,Osako, Takao,Uozumi, Yasuhiro
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- Structure–Activity Relationships of 1-Benzoylazulenes at the OX1 and OX2 Orexin Receptors
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We previously demonstrated the potential of di- or trisubstituted azulenes as ligands (potentiators, weak agonists, and antagonists) of the orexin receptors. In this study we investigated 27 1-benzoylazulene derivatives, uncovering seven potentiators of t
- Turku, Ainoleena,Leino, Teppo O.,Karhu, Lasse,Yli-Kauhaluoma, Jari,Kukkonen, Jyrki P.,Wallén, Erik A. A.,Xhaard, Henri
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p. 965 - 981
(2019/04/10)
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- Nickel-catalyzed aminocarbonylation of aryl halides using carbamoylsilane as an amide source
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The nickel-catalyzed aminocarbonylation of aryl halides using carbamoylsilane as an amide source is developed. The procedure can prepare both tertiary and secondary amides, and is applicable to various carbamoylsilanes and aryl halides containing differen
- Wen, Xue-Ping,Han, Yu-Ling,Chen, Jian-Xin
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p. 45107 - 45112
(2017/10/13)
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- Facile Access to Amides from Oxygenated or Unsaturated Organic Compounds by Metal Oxide Nanocatalysts Derived from Single-Source Molecular Precursors
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Oxidative amidation is a valuable process for the transformation of oxygenated organic compounds to valuable amides. However, the reaction is severely limited by the use of an expensive catalyst and limited substrate scope. To circumvent these limitations, designing a transition-metal-based nanocatalyst via more straightforward and economical methodology with superior catalytic performances with broad substrate scope is desirable. To resolve the aforementioned issues, we report a facile method for the synthesis of nanocatalysts NiO and CuO by the sol-gel-assisted thermal decomposition of complexes [Ni(hep-H)(H2O)4]SO4 (SSMP-1) and [Cu(μ-hep)(BA)]2 (SSMP-2) [hep-H = 2-(2-hydroxylethyl)pyridine; BA = benzoic acid] as single-source molecular precursors (SSMPs) for the oxidative amidation of benzyl alcohol, benzaldehyde, and BA by using N,N-dimethylformamide (DMF) as the solvent and as an amine source, in the presence of tert-butylhydroperoxide (TBHP) as the oxidant, at T = 80 °C. In addition to nanocatalysts NiO and CuO, our previously reported Co/CoO nanocatalyst (CoNC), derived from the complex [CoII(hep-H)(H2O)4]SO4 (A) as an SSMP, was also explored for the aforementioned reaction. Also, we have carefully investigated the difference in the catalytic performance of Co-, Ni-, and Cu-based nanoparticles synthesized from the SSMP for the conversion of various oxygenated and unsaturated organic compounds to their respective amides. Among all, CuO showed an optimum catalytic performance for the oxidative amidation of various oxygenated and unsaturated organic compounds with a broad reaction scope. Finally, CuO can be recovered unaltered and reused for several (six times) recycles without any loss in catalytic activity.
- Mohammad, Akbar,Chandra, Prakash,Ghosh, Topi,Carraro, Mauro,Mobin, Shaikh M.
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p. 10596 - 10608
(2017/09/12)
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- A use of the carboxamides aryl carbonyl aminolysis method of preparing amide
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The invention discloses a method for preparing amides via a decarbonylation ammonolysis reaction of aryl ester and formamide. The method comprises the following steps: dissolving a palladium catalyst, aryl ester and formamide in a solvent, and stirring fo
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Paragraph 0030; 0032-0035
(2016/10/10)
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- Heterogeneous recyclable nano-palladium catalyzed amidation of esters using formamides as amine sources
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Catalyzed by supported palladium nanoparticles, a decarbonylative amidation reaction between various aryl esters and formamides by C-O bond activation has been developed for the synthesis of amides. The catalyst can be reused and shows high activity after
- Bao, Yong-Sheng,Wang, Lili,Jia, Meilin,Xu, Aiju,Agula, Bao,Baiyin, Menghe,Zhaorigetu, Bao
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p. 3808 - 3814
(2016/07/07)
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- General and efficient oxidative amidation of benzyl alcohols with amines using diacetoxyiodobenzene and TBHP
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A facile oxidative coupling of alcohols and amines to construct amides was developed using DIB as a catalyst and aqueous tert-butyl hydroperoxide as an oxidant. Various secondary and tertiary amides were prepared in good yield utilizing inexpensive and readily available reagents under mild reaction condition. The reaction involved operational simplicity, metal free oxidation, and wide functional group tolerance as attractive features.
- Sutar, Yogesh B.,Bhagat, Saket B.,Telvekar, Vikas N.
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p. 6768 - 6771
(2016/02/03)
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- Oxidative coupling of methylamine with an aminyl radical: Direct amidation catalyzed by I2/TBHP with HCl
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Oxidative coupling of methylamines with an aminyl radical to construct amides was developed in the presence of an I2/TBHP catalyst under acidic conditions via the two cleavages of the sp3 C-N bond of aryl-methylamines and the sp2 C-N bond of N-substituted formamides respectively. This transition-metal-free protocol provides a novel synthetic tool for the construction of N-substituted amides and a series of arylamides can be easily obtained with good yields. This journal is the Partner Organisations 2014.
- Gao, Lingfeng,Tang, Haoming,Wang, Zhiyong
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supporting information
p. 4085 - 4088
(2014/04/03)
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- Electrochemical synthesis of amides: Direct transformation of methyl ketones with formamides
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A direct transformation from methyl ketones to secondary or tertiary amides has been developed through a novel electrochemical approach and a wide scope of formamides could be utilized as the amide sources. This transformation was promoted by in situ generated iodine through electrolysis of sodium iodide under mild, metal-free conditions. This electrochemical procedure could avoid the use of stoichiometric iodine and afforded the target products in good to excellent yields.
- Huang, Haolai,Yuan, Gaoqing,Li, Xianwei,Jiang, Huanfeng
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supporting information
p. 7156 - 7159
(2013/12/04)
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- Copper-catalyzed formation of N,N-dimethyl benzamide from nitrile and DMF under an O2 atmosphere
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Amidation of nitrile with N,N-dimethylformamide (DMF) was catalyzed by Cu2O with 1,10-phenanthroline as a ligand under an oxygen atmosphere. A variety of N,N-dimethyl benzamides were obtained in yields up to 84%.
- Hu, Chenxu,Yan, Xufei,Zhou, Xiangge,Li, Zhengkai
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p. 8179 - 8182
(2013/12/04)
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- Copper catalyzed cross-coupling reactions of carboxylic acids: An expedient route to amides, 5-substituted γ-lactams and α-acyloxy esters
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A convenient and recyclable catalytic protocol for the synthesis of N,N-dimethyl substituted amides, 5-substituted γ-lactams and α-acyloxy ethers from carboxylic acids using CuO nanoparticles and TBHP is described.
- Priyadarshini,Amal Joseph,Lakshmi Kantam
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p. 18283 - 18287
(2013/10/21)
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- Direct amidation of alcohols with N-substituted formamides under transition-metal-free conditions
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Go tandem! The first example of the direct amidation of alcohols with N-substituted formamides has been developed. A series of tertiary amides, including the challenging N,N-dimethyl-substituted amides, were obtained in moderate to good yields under transition-metal-free conditions (see scheme). TBHP=tert-butyl hydroperoxide. Copyright
- Xu, Kun,Hu, Yanbin,Zhang, Sheng,Zha, Zhenggen,Wang, Zhiyong
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supporting information; experimental part
p. 9793 - 9797
(2012/09/05)
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- Metal-free n-Bu4NI-catalyzed direct synthesis of amides from alcohols and N,N-disubstituted formamides
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A facile and efficient protocol for the synthesis of amides has been developed in the absence of transition metals. The reaction was performed with a catalytic amount of n-Bu4NI and aqueous TBHP as an oxidant. Various alcohols with N,N-disubstituted formamides were examined to furnish the desired products in good yields.
- Li, Huamin,Xie, Jin,Xue, Qicai,Cheng, Yixiang,Zhu, Chengjian
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supporting information
p. 6479 - 6482,4
(2012/12/12)
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- Cross coupling of acyl and aminyl radicals: Direct synthesis of amides catalyzed by Bu4NI with TBHP as an oxidant
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A radical solution: A Bu4NI/tert-butyl hydroperoxide (TBHP) catalyzed synthesis of amides through a cross-coupling reaction between acyl and aminyl radicals is described. This method involves the combination of aldehyde C-H bond functionalization and decarbonylation of N,N-disubstituted formamides (see scheme). The cross-coupling is metal-free, has a wide substrate scope, operational simplicity, and gives high yields on scale-up. Copyright
- Liu, Zhaojun,Zhang, Jie,Chen, Shulin,Shi, Erbo,Xu, Yuan,Wan, Xiaobing
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experimental part
p. 3231 - 3235
(2012/05/05)
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- Facile preparation of aromatic esters from aromatic bromides with ethyl formate or DMF and molecular iodine via aryllithium
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Various aromatic bromides were treated with n-BuLi and subsequently with ethyl formate, followed by the reaction with ethanol and molecular iodine in the presence of K2CO3 to provide the corresponding aromatic ethyl esters in good yields. Moreover, aromatic bromides could be transformed into the corresponding aromatic methyl esters in good yields by the treatment with n-BuLi and subsequently with DMF, followed by the reaction with methanol, molecular iodine, and K2CO3. Some aromatics could be also converted into the corresponding aromatic esters in good yields by the treatment with n-BuLi, and subsequently with ethyl formate or DMF, followed by the reaction with molecular iodine and K2CO3. The present reactions offer a novel route for the transition-metal-free, carbon-monoxide-free, and therefore environmentally benign one-pot conversion of aromatic bromides and aromatics into aromatic esters.
- Ushijima, Sousuke,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 4701 - 4709
(2012/07/28)
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- Aminocarbonylation of aryl halides using a nickel phosphite catalytic system
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(Formula Presented) The nickel and phosphite catalytic system with sodium methoxide enables a very efficient aminocarbonylation reaction to be performed between aryl iodides or bromides and N,N-dimethylformamide (DMF). Phosphite ligand 1, which is very st
- Ju, Jinhun,Jeong, Miso,Moon, Jeongju,Hyun, Min Jung,Lee, Sunwoo
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p. 4615 - 4618
(2008/03/13)
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- Direct carbamoylation of aryl halides
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(Equation presented) A carbamoylsilane is shown to carry out the direct carbamoylation of aryl chlorides, bromides, and iodides under catalysis by phosphinepalladium-(0) complexes.
- Cunico, Robert F.,Maity, Bikash C.
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p. 4357 - 4359
(2007/10/03)
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- Orthoamides, LVIII. Condensation reactions of CH2-acidic compounds with orthoamides of carboxylic acids and alkyne carboxylic acids
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The orthoamide derivatives 1s and 2e were prepared from the guanidinium salt 7a and the appropriate carbanions. Cleavage of the orthoamide 2e with benzoyl chloride affords the amidinium salt 10a, which can be transformed into the amidinium salt 10b by an
- Kantlehner, Willi,Haug, Erwin,Stieglitz, Rüdiger,Frey, Wolfgang,Kress, Ralf,Mezger, Jochen
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p. 399 - 419
(2007/10/03)
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- A novel transformation of 2-acetylthiophene and its halogen derivatives under Vilsmeier reaction conditions
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Under conditions of the Vilsmeier reaction either β-chloro-β-(2-thienyl)acrylic aldehydes or N,N-dimethyl-2-thiophenecarboxamides can be synthesised from 2-acetylthiophenes depending on the reaction temperature and time.
- Shirinian, Valerii Z.,Belen'kii, Leonid I.,Krayushkin, Mikhail M.
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- Process for preparing 5-aroyl-2,3-dihydro-1H-pyrrolizine-1,1-dicarboxylates (I) and intermediates therefor
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5-Aroyl-2,3-dihydro-1H-pyrrolizine-1,1-dicarboxylates of the formula STR1 are prepared from 2-aroylpyrroles. Hydrolysis and mono-decarboxylation of these compounds affords ketorolac and related compounds.
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- ELECTROPHILIC AMINATION OF ACYL ANION EQUIVALENTS: MILD OXIDATION OF ALDEHYDES TO AMIDES VIA O-(TRIMETHYLSILYL)ALDEHYDE CYANOHYDRIN ANIONS
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The O-(trimethylsilyl)aldehyde cyanohydrin anions 4a-p(1-)*Li(1+) react with 5 to the amines 6.This electrophilic amination corresponds to a mild and specific oxidation of the aldehydes 1a-p to the amides 7a-p.
- Boche, Gernot,Bosold, Ferdinand,Niessner, Manfred
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p. 3255 - 3256
(2007/10/02)
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- Preparation of 5-aroylpyrrole-2-acetic acid derivatives
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The interaction of a 2-aryldithiolanium cation with an appropriate pyrrole-2-acetic acid derivative to give a 5-[2-aryl-2-(1,3-dithiolanyl)]pyrrole-2-acetic acid derivative which is then converted to the corresponding 5-aroylpyrrole-2-acetic acid derivative.
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