- Selective electrochemical oxidation of aromatic hydrocarbons and preparation of mono/multi-carbonyl compounds
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A selective electrochemical oxidation was developed under mild condition. Various mono-carbonyl and multi-carbonyl compounds can be prepared from different aromatic hydrocarbons with moderate to excellent yield and selectivity by virtue of this electrochemical oxidation. The produced carbonyl compounds can be further transformed into α-ketoamides, homoallylic alcohols and oximes in a one-pot reaction. In particular, a series of α-ketoamides were prepared in a one-pot continuous electrolysis. Mechanistic studies showed that 2,2,2-trifluoroethan-1-ol (TFE) can interact with catalyst species and generate the corresponding hydrogen-bonding complex to enhance the electrochemical oxidation performance. [Figure not available: see fulltext.]
- Li, Zhibin,Zhang, Yan,Li, Kuiliang,Zhou, Zhenghong,Zha, Zhenggen,Wang, Zhiyong
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p. 2134 - 2141
(2021/09/29)
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- Diversification of α-ketoamides: Via transamidation reactions with alkyl and benzyl amines at room temperature
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A wide range of N-tosyl α-ketoamides underwent transamidation with various alkyl amines in the absence of a catalyst, base, or additive. On the other hand, transamidation in N-Boc α-ketoamides was achieved in the presence of Cs2CO3. The reactions proceede
- Junaid, Qazi Mohammad,Kandasamy, Jeyakumar,Popuri, Sureshbabu,Sabiah, Shahulhameed,Singh, Shweta
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p. 7134 - 7140
(2021/08/30)
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- Synthesis of aliphatic α-ketoamides from α-substituted methyl ketones: Via a Cu-catalyzed aerobic oxidative amidation
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α-Ketoamides are an important key functional group and have been used as versatile and valuable intermediates and synthons in a variety of functional group transformations. Synthetic methods for making aryl α-ketoamides as drug candidates have been greatly improved through metal-catalyzed aerobic oxidative amidations. However, the preparation of alkyl α-ketoamides through metal-catalyzed aerobic oxidative amidations has not been reported because generating α-ketoamides from aliphatic ketones with two α-carbons theoretically provides two distinct α-ketoamides. Our strategy is to activate the α-carbon by introducing an N-substituent at one of the two α-positions. The key to this strategy is how heterocyclic compounds such as triazoles and imidazoles affect the selectivity of the synthesis of the alkyl α-ketoamides. From this basic concept, and by optimizing the reaction and elucidating the mechanism of the synthesis of aryl α-ketoamides via a copper-catalyzed aerobic oxidative amidation, we prepared fourteen aliphatic α-ketoamides in high yields (48-84%). This journal is
- Cha, Hyojin,Chai, Jin Young,Chi, Dae Yoon,Kim, Hyeong Baik
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p. 4320 - 4326
(2021/05/31)
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- Rapid assembly of α-ketoamides through a decarboxylative strategy of isocyanates with α-oxocarboxylic acids under mild conditions
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A simple and practical method for α-ketoamide synthesis via a decarboxylative strategy of isocyanates with α-oxocarboxylic acids is described. The reaction proceeds at room temperature under mild conditions without an oxidant or an additive, showing good substrate scope and functional compatibility. Moreover, the applicability of this method was further demonstrated by the synthesis of various bioactive molecules and different application examples through a two-step one-pot operation.
- Huang, Junjie,Liang, Baihui,Chen, Xiuwen,Liu, Yifu,Li, Yawen,Liang, Jingwen,Zhu, Weidong,Tang, Xiaodong,Li, Yibiao,Zhu, Zhongzhi
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supporting information
p. 4783 - 4787
(2021/06/11)
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- Synthesis method of alpha-ketoamide compound
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The invention discloses a synthesis method of an alpha-ketoamide compound. The preparation method comprises the following steps of: taking an isocyanate compound as shown in a formula I and a benzoylformic acid compound as shown in a formula II as raw mat
- -
-
Paragraph 0124-0130
(2020/12/09)
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- Amine-Mediated Bond Cleavage in Oxidized Lignin Models
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Introducing amines/ammonia into lignin cracking will allow novel bond cleavage pathways. Herein, a method of amines/ammonia-mediated bond cleavage in oxidized lignin β-O-4 models was studied using a copper catalyst at room temperature, demonstrating the effect of the amine source on the selectivity of products. For primary and secondary aliphatic amines, lignin ketone models underwent oxidative Cα?Cβ bond cleavage and Cα?N bond formation to generate aromatic amides. For ammonia, the competition between oxygen and ammonia determined the selectivity between Cα?N and Cβ?N bond formation, generating amides and α-keto amides, respectively. For tertiary amines, the lignin models underwent oxidative Cα?Cβ bond cleavage to benzoic acids. Control experiments indicated that amines act as nucleophiles attacking at the Cα or Cβ position of the oxidized β-O-4 linkage to be cleaved. This study represents a novel example that the breakage of oxidized lignin model can be regulated by amines with a copper catalyst.
- Li, Hongji,Liu, Meijiang,Liu, Huifang,Luo, Nengchao,Zhang, Chaofeng,Wang, Feng
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p. 4660 - 4665
(2020/07/04)
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- Photocatalytic preparation method of alpha-ketoamide compound
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The invention discloses a preparation method of an alpha-ketoamide compound, particularly to a method for preparation of an alpha-ketoamide compound by photocatalysis technology. The preparation method specifically includes the steps of: adding alpha-keto
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-
Paragraph 0070-0072
(2020/01/25)
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- Visible-light-mediated metal-free decarboxylative acylations of isocyanides with α-oxocarboxylic acids and water leading to α-ketoamides
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An efficient visible-light-promoted approach for preparing α-ketoamides from α-oxocarboxylic acids, isocyanides and water is disclosed. The present transformation could be achieved under mild and metal-free conditions through a sequence of decarboxylation
- Lv, Yufen,Bao, Pengli,Yue, Huilan,Li, Jiang-Sheng,Wei, Wei
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supporting information
p. 6051 - 6055
(2019/11/20)
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- 1,2-dicarbonyl compound and synthesis method thereof
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The invention discloses a method for synthesizing a 1,2-dicarbonyl compound (1,2-dicarbonylamide or alpha-diketone compound), wherein 1,2-dicarbonyl thioester compounds used as 1,2-dicarbonyl reagentsreact with amine compounds or boric anhydride compounds under appropriate conditions to respectively synthesize a series of 1,2-dicarbonyl compounds. According to the present invention, the 1,2-dicarbonyl compound is obtained by using the stable 1,2-dicarbonyl thioester compound as the dicarbonylation reagent through one-step construction under mild conditions, such that the disadvantage that thetraditional method uses the unstable alpha-carbonyl acyl chloride to synthesize the 1,2-dicarbonyl compound is avoided.
- -
-
Paragraph 0055; 0072-0075
(2019/10/01)
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- Synthesis of α-Ketoamides from β-Ketonitriles and Primary Amines: A Catalyst-Free Oxidative Decyanation–Amidation Reaction
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AN oxidative decyanation–amidation of β-ketonitriles and primary amines readily occurs using hydrogen peroxide sodium carbonate adduct (Na2CO3·1.5H2O2), K2CO3, and 1,4-dioxane. This reactio
- Zhang, Ya-Kai,Wang, Bin
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p. 5732 - 5735
(2019/08/27)
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- Diverse Oxidative C(sp2)-N Bond Cleavages of Aromatic Fused Imidazoles for Synthesis of α-Ketoamides and N-(pyridin-2-yl)arylamides
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An efficient and chemoselective C(sp2)-N bond cleavage of aromatic imidazo[1,2-a]pyridine molecules is developed. A broad scope of amide compounds such as α-ketoamides and N-(pyridin-2-yl)arylamides are afforded as the final products in up to quantitative yields. Diverse C-N bond cleavages are controlled by the oxidative species used in this transformation, with various amide products afforded in a chemoselective fashion. A preliminary study indicated that some α-ketoamides exhibit anti-Tobacco Mosaic Virus activity for potential use in plant protection.
- Xu, Fangzhou,Wang, Yanyan,Xun, Xiwei,Huang, Yun,Jin, Zhichao,Song, Baoan,Wu, Jian
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p. 8411 - 8422
(2019/05/17)
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- Preparation method of alpha-carbonyl amide derivatives
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The invention discloses a preparation method of alpha-carbonyl amide derivatives. According to the method, pyridino-aminoimidazole compounds and water are subjected to ring-opening reaction under theaction of an oxidizing agent, meanwhile, oxygen atoms ar
- -
-
Paragraph 0020-0022
(2019/01/14)
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- UV Assisted High-Efficient Synthesis of α-Ketoamides using Air Promoted by A Non-Metal Catalyst in Aqueous Solution
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Presented here is the first example of UV (λ=210 nm) promoted procedure proceeding in aqueous media at room temperature using ambient air as the oxidant for efficient synthesis of an array of α-ketoamides of all types using a non-metal catalyst N-iodosuccinimide with a loading of 20 mol%. With UV, oxygen in the air was efficiently utilized as the green oxidant, some control experiments were carried out and a plausible mechanism was proposed, disclosing that in aqueous solution, the oxidation process was actually triggered by dioxygen radical anion (O2.?), while not molecular oxygen. A variety of secondary amines and primary amines as well as ammonia were employed as the amine moieties, and the desired product primary-, secondary-, and tertiary α-ketoamides were afforded in good to excellent yields of up to 96 %.
- Li, Jianhui,He, Shaopo,Zhang, Kuan,Quan, Ziyi,Shan, Qiheng,Sun, Zhongliang,Wang, Bo
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p. 4868 - 4873
(2018/10/15)
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- nBu4NI-Mediated oxidation of methyl ketones to α-ketoamides: using ammonium, primary and secondary amine-salt as an amine moiety
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Presented here is the first example of synthesizing an array of primary-, secondary-, and tertiary-α-ketoamides with a non-metal catalyst nBu4NI from methyl ketones and inexpensive readily available amine/ammonium salts; the reactions proceeded smoothly under mild conditions, TBHP was used as an oxidant and the corresponding α-ketoamides were afforded in moderate to excellent yields.
- Wang, Dan,Zhang, Kuan,Jia, Luhan,Zhang, Danting,Zhang, Yue,Cheng, Yujia,Lin, Chang,Wang, Bo
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p. 3427 - 3434
(2017/04/24)
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- Novel synthesis of tetrahydro-1H-pyrrolo[1,2-a]imidazol-2-ones via decarboxylative cyclization reaction of α-amino acids and α-ketoamides
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An efficient and practical method was developed for the synthesis of tetrahydro-1H-pyrrolo[1,2-a]imidazol-2-ones based on the decarboxylative cyclization reaction of α-ketoamides and proline. In most cases, tetrahydro-1H-pyrrolo[1,2-a]imidazol-2-ones were obtained with perfect diastereoselectivity to give trans-isomer in excellent yield.
- Wu, Jia-shou,Jiang, Hua-jiang,Yang, Jian-guo,Jin, Zheng-neng,Chen, Ding-ben
-
supporting information
p. 546 - 551
(2017/01/16)
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- In situ generated Pd(0) nanoparticles stabilized by bis(aryl)acenaphthenequinone diimines as catalysts for aminocarbonylation reactions in water
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Aminocarbonylation of aryl iodides with aromatic and aliphatic amines, leading to formation of the corresponding amides, was efficiently carried out in water under 1?atm of CO using palladium nanoparticles (Pd NPs) formed in situ from [PdCl2(Ar2-BIAN)] complexes. The role of Ar2-BIAN ligands in the stabilization of Pd NPs was evidenced. The nature of the catalytically active species was confirmed by poisoning experiments, which highlighted that the catalyst is actually in the form of Pd NPs rather than soluble palladium complexes. In the aminocarbonylation of iodobenzene with substituted anilines good yields of amides were obtained, although the activity was depleted by the presence of substituents in the ortho positions of the aniline. On the other hand, in the reaction with aliphatic amines α-ketoamides were formed in addition to the amides. The selectivity towards α-ketoamides was increased by increasing the CO pressure to 10?atm, at equimolar amounts of PhI and amine. Pd NPs were successfully recovered after the catalytic reaction and recycled in five subsequent runs with only a marginal loss of activity after the fourth cycle.
- Wójcik,Rosar,Gniewek,Milani,Trzeciak
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p. 322 - 331
(2016/12/07)
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- Cu(i)-Functionalized SBA-16: An efficient catalyst for the synthesis of α-ketoamides under moderate conditions
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An efficient catalyst based on the cage-like mesoporous material SBA-16 as the support and Cu(i) as active sites has been successfully prepared. The catalyst demonstrated high catalytic activity (up to 88%) in the direct oxidative synthesis of α-ketoamides between acetophenone and piperidine, employing O2 from open air as the oxidant without other additives. A heterogeneous catalyst was applied in this reaction for the first time, and the catalyst could be easily separated from the reaction system by filtration and reused several times without a significant loss of activity.
- Zhang, Xueyao,Yang, Honglei,Huo, Yong,Li, Jing,Ma, Jianxin,Ma, Jiantai
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p. 8972 - 8983
(2016/06/09)
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- Alkyl halide-free heteroatom alkylation and epoxidation facilitated by a recyclable polymer-supported oxidant for the in-flow preparation of diazo compounds
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Highly reactive metal carbenes, generated from simple ketones via diazo compounds, including diazoamides and -phosphonates, using a recyclable reagent inflow, are transient but versatile electrophiles for heteroatom alkylation reactions and for epoxide formation. The method produces no organic waste, with the only byproducts being water, KI and nitrogen, without the attendant hazards of isolation of intermediate diazo compounds.
- Nicolle, Simon M.,Hayes, Christopher J.,Moody, Christopher J.
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supporting information
p. 4576 - 4579
(2015/03/18)
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- A palladium(II)-catalyzed synthesis of α-ketoamides via chemoselective aroyl addition to cyanamides
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An acyl moiety generated from α-oxocarboxylic acids via decarboxylation undergoes a palladium-catalyzed chemoselective insertion into organic cyanamides to afford N-monosubstituted α-ketoamides.
- Guin, Srimanta,Rout, Saroj Kumar,Gogoi, Anupal,Ali, Wajid,Patel, Bhisma K.
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p. 2559 - 2565
(2014/09/29)
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- Coupling of methyl ketones and primary or secondary amines leading to α-ketoamides
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A metal-free oxidative coupling of methyl ketones and primary or secondary amines to α-ketoamides has been developed. Four intermediates, α-iodoketone, α-aminoketone, iminium intermediate, and α-hydroxy amine have been identified through a series of control experiments. The atom-economic methodology can be scaled-up, tolerates a variety of functional groups, and is operationally simple.
- Wei, Wei,Shao, Ying,Hu, Huayou,Zhang, Feng,Zhang, Chao,Xu, Yuan,Wan, Xiaobing
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p. 7157 - 7165
(2012/11/07)
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- Ugi four-component condensation with two cleavable components: the easiest synthesis of 2,N-diarylglycines
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The Ugi four-component condensation between anilines, aromatic aldehydes, isocyanides, and α-oxoacids afforded the expected adducts which were cleaved in mild conditions to give 2,N-diarylglycines in high yields.
- Faggi, Cristina,Neo, Ana G.,Marcaccini, Stefano,Menchi, Gloria,Revuelta, Julia
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p. 2099 - 2102
(2008/09/17)
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- Rapid synthesis of α-ketoamides using microwave irradiation- simultaneous cooling method
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Microwave-assisted acyl chloride-isonitrile condensation and CaCO 3-mediated hydrolysis constitute a one-pot, 2-minute process to prepare α-ketoamides.
- Chen, Jack J.,Deshpande, Seema V.
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p. 8873 - 8876
(2007/10/03)
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- Ring Cleavage of 1,2,3-Triazolium Ions with Nucleophiles
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The 1,2,3-triazolium salts 1 react with a variety of nucleophiles to give products of ring scission like 2-5.The new 1,2,3-triazolium reaction most probably does not follow the pattern known in the case of isoxazolium and furazanium salts.
- Moderhack, Dietrich
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p. 1271 - 1274
(2007/10/02)
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- SINTESI E CONFIGURAZIONE DI ACIDI α-IDRAZONOFENILACETICI
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The synthesis of some α-hydrazonophenylacetic acids (II) by direct condensation of phenylglyoxylic acid with hydrazine or monosubstituted hydrazines and subsequent conversion into the α-alkoxycarbonylhydrazonophenylacetic acids (IV) according to three dif
- Monguzzi, R.,Scarpitta, G.,Ventura, P.,Pifferi, G.
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p. 394 - 404
(2007/10/02)
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