- Synthesis and X-ray structure of N-phenyl phenylglyoxamide
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The title compound (C14H11NO2) is monoclinic with a = 13.579(2), b = 5.297(1), c = 16.455(2) A, β = 98.11(2)°, Z = 4, and space group P21/n. The significant structural features lie in the two carbonyl groups of the glyoxamide which are oriented antiperiplanar to each other [-163.6(3)°]. The central bond C(1)-C(2) is 1.545(4) A. The observed conformation is stabilized by intramolecular hydrogen bonds.
- Boryczka, Stanislaw,Suwinska, Kinga,Le Guillanton, Georges,Do, Quang Tho,Elothmani, Driss
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- A novel synthesis of diversely functionalized 1,2,4-triones through the homo- and cross-coupling reactions of β-keto sulfoxonium ylides
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A novel synthesis of functionalized 1,2,4-triones via an oxidative homo-coupling of β-keto sulfoxonium ylides is presented. Preliminary mechanistic study reveals that the formation of the 1,2,4-trione product involves the in situ generation of an α-keto aldehyde intermediate via Cu(II)-promoted oxidative decomposition of β-keto sulfoxonium ylide followed by its coupling with the second molecule of ylide. Based on this intrinsic mechanism, a formal cross-coupling reaction was designed and successfully realized, from which more diversely functionalized 1,2,4-triones were synthesized with high efficiency. Compared with literature methods, notable features of this novel synthetic protocol include easily accessible and safe substrates, excellent functional group tolerance, convenient procedure, mild reaction conditions, and ready scalability.
- Chen, Xi,Wang, Muhua,Zhang, Xinying,Fan, Xuesen
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- A Pd-catalyzed one-pot cascade consisting of C-C/C-O/N-N bond formation to access benzoxazine fused 1,2,3-triazoles
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A Pd-catalyzed one-pot cascade consisting of C-C/C-O/N-N bond formation to access clinically important fused 1,2,3-triazoles using N-aryl-α-(tosylhydrazone)acetamides with isocyanide has been developed. Besides, various substitutions on the N-aryl part of
- Soam, Pooja,Gaba, Hashmita,Mandal, Debasish,Tyagi, Vikas
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p. 9936 - 9945
(2021/12/07)
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- Desulfurizing agent for thioamides
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Thioamides treated with thionyl chloride in an ionic liquid were successfully converted into amides.
- Polushina,Zavarzin,Krayushkin,Rodionova,Yarovenko
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p. 383 - 385
(2021/03/03)
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- Ru-g-C3N4as a highly active heterogeneous catalyst for transfer hydrogenation of α-keto amide into β-aminol or α-hydroxyl amide
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This work reports a sustainable route for the catalytic transfer hydrogenation (CTH) of α-keto amide into β-aminol via an efficient heterogeneous catalyst wherein ruthenium is incorporated on an active graphite sheet of a carbon nitride support (Ru-g-C3N4). Other different metals like Ni or Pd were also screened with the same support but none of them showed efficient activity. Although, partial hydrogenation of ketone to alcohol has also been observed based on the optimization of the reaction parameters using all of the above catalysts. The catalyst has been characterized using field emission gun scanning electron microscopy (FEG-SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infra-red (IR) spectroscopy and thermogravimetric analysis (TGA). Furthermore, the catalyst has been recycled and further characterized and does not show any significant changes in its reactivity for the CTH process. Ru-g-C3N4 as a recyclable heterogenous catalyst has been used for the first time for the CTH of α-keto amide into β-aminol, making the process sustainable because economical and environmentally benign isopropyl alcohol is used as a solvent system. The proposed catalytic system shows a wide scope of substrates for α-hydroxyamide and β-aminol derivatives, which were confirmed from 1H and 13C-NMR. This journal is
- Bhanage, Bhalchandra M.,Chaurasia, Shivkumar R.,Mishra, Ashish A.
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supporting information
p. 10578 - 10585
(2020/07/14)
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- Synthesis of α-ketoamides using potassium superoxide (KO2) as an oxidizing agent
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A simple and convenient method for the synthesis of α-ketoamides by the oxidation of aryl acetamides using potassium superoxide (KO2) as an oxidizing agent is disclosed here. The scope of the developed method is successfully tested with fifteen substrates. In addition, the utility of method has been demonstrated by synthesizing an orexin receptor antagonist, a medicinally interesting compound.
- Vasudevan,Routholla, Ganesh,Teja Illa, Giri,Reddy, D. Srinivasa
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- Synthetic method of alpha-keto amide compound
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The invention discloses a synthesis method of an alpha-keto amide compound, which comprises the following steps: mixing a benzoyl azide compound as shown in a chemical formula I with a benzoyl formicacid compound as shown in a chemical formula II, and reacting to obtain an alpha-keto amide compound as shown in a chemical formula III; in the formula, R1 is a monosubstituted or polysubstituted group on a benzene ring; R2 is a group that is not H; the synthesis method can be used for efficiently synthesizing the functionalized alpha-ketoamide compound, has the advantages of simple synthesis steps, safety in operation, good compatibility of the synthesis method to functional groups and high atom economy, and is easy for industrial synthesis.
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Paragraph 0069-0074
(2020/09/23)
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- Pd(OAc)2-Catalyzed Asymmetric Hydrogenation of α-Iminoesters
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An efficient Pd(OAc)2-catalyzed asymmetric hydrogenation of α-iminoesters was realized for the first time at 1 atm hydrogen pressure and room temperature. Pd(OAc)2, a less expensive Pd salt with low toxicity, was found to be the most suitable catalyst precursor rather than Pd(TFA)2 which is usually the catalyst of choice for homogeneous asymmetric hydrogenation. The chiral α-arylglycine fragments are widely found in many chiral products and bioactive molecules.
- Chen, Jianzhong,Li, Feilong,Wang, Fang,Hu, Yawen,Zhang, Zhenfeng,Zhao, Min,Zhang, Wanbin
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p. 9060 - 9065
(2019/11/19)
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- Catalyst- and Additive-Free Chemoselective Transfer Hydrogenation of α-Keto Amides to α-Hydroxy Amides by Sodium Formate
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A catalyst- and additive-free chemoselective transfer hydrogenation of α-keto amides to α-hydroxy amides is easily achieved by using sodium formate as a hydrogen source. The utility of this method is demonstrated by gram-scale synthesis and transformation of the resultant α-hydroxy amides into polysubstituted acetamides and 2-arylindole derivatives. Control experiments suggest that the NH group of α-keto amides is crucial for the chemoselective reduction through the formation of hydrogen bonds.
- Hao, Feiyue,Gu, Zhenyu,Liu, Guyue,Yao, Wubing,Jiang, Huajiang,Wu, Jiashou
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p. 5985 - 5991
(2019/09/10)
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- Zirconium-MOF-catalysed selective synthesis of α-hydroxyamide via the transfer hydrogenation of α-ketoamide
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This work reports the synthesis of α-hydroxy amide and its derivatives using zirconium-based metal-organic frameworks (Zr-MOFs). The Zr-MOF was prepared using a ligand containing different functionalities as a linker with different porosities. The catalyst efficiently facilitated the transfer hydrogenation of α-ketoamide to α-hydroxyamide. The reaction involved a green hydrogen source, namely isopropyl alcohol, which also acted as a solvent. The role of the ligand in the catalyst was optimized for the selective conversion of α-ketoamide to α-hydroxyamide. UiO-66 (Zr) crystal was efficiently used for the first time for the hydrogenation of α-ketoamide to α-hydroxyamide. The catalyst was recovered and recycled five times without any loss in activity and selectivity performance. The morphology, activity and stability of the UiO-66 (Zr) catalyst were analyzed using field emission gun scanning electron microscopy (FEG-SEM), X-ray diffraction (XRD), infra-red (IR) spectroscopy and thermogravimetric analysis (TGA). The existence of α-hydroxyamide and its derivatives was confirmed from 1H and 13C-NMR.
- Mishra, Ashish A.,Bhanage, Bhalchandra M.
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p. 6160 - 6167
(2019/04/25)
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- Synthesis and Properties of 1-Acyl Triazenes
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1-Acyl triazenes can be prepared by acid-catalyzed hydration, gold/iodine-catalyzed oxidation, or oxyhalogenation of 1-alkynyl triazenes. Crystallographic analyses reveal a pronounced effect of the acyl group on the electronic structure of the triazene fu
- Landman, Iris R.,Acu?a-Bolomey, Emilio,Scopelliti, Rosario,Fadaei-Tirani, Farzaneh,Severin, Kay
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p. 6408 - 6412
(2019/09/06)
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- Copper-catalyzed oxidative cleavage of Passerini and Ugi adducts in basic medium yielding α-ketoamides
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The aerobic oxidative cleavage of Passerini and Ugi adducts in the presence of base and copper(i) iodide is studied in detail. The oxidative cleavage yields α-ketoamides along with acids and amides from Passerini and Ugi adducts respectively. Mechanistic investigations revealed that the reaction proceeds via a radical pathway involving molecular oxygen. Control experiments with 18O-labeled Passerini adducts confirmed that molecular oxygen is the source of oxygen in α-ketoamides. A variety of Passerini and Ugi adducts were studied to explore the effect of substitution. Overall, the present study provides an insight into the reactivity of Passerini and Ugi adducts in strong basic conditions along with a method to prepare α-ketoamides.
- Ghoshal, Anirban,Ambule, Mayur D.,Sravanthi, Revoju,Taneja, Mohit,Srivastava, Ajay Kumar
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p. 14459 - 14474
(2019/10/01)
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- Iodine-mediated aryl transfer reaction from arylhydrazine hydrochlorides to nitriles
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An iodine-promoted, metal-, base-, and solvent-free cross-coupling reaction was developed for the synthesis of various useful secondary amides via an aryl N-addition reaction of aryl groups to cyano groups. This aryl transfer reaction proceeds with arylhydrazine hydrochlorides serving as the aryl donors. A labelling experiment shows that the N atom in the product comes from the cyano group of the nitriles, which are low in cost. A plausible radical-driven mechanism is also proposed.
- Zhang, Zhiguo,Li, Xiang,Li, Yinghua,Guo, Yan,Zhao, Xunan,Yan, Yan,Sun, Kai,Zhang, Guisheng
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supporting information
p. 3628 - 3635
(2019/05/29)
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- Facile photochemical synthesis of α-ketoamides and quinoxalines from amines and benzoylacetonitrile under mild conditions
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A selective protocol for the synthesis of either α-ketoamides or quinoxaline derivatives under the same reaction conditions has been achieved simply by varying substitution number of amino-groups. The method features metal-free, room temperature and broad substrate scopes as well as no extra oxidant. This process applies to various substituent groups and gives products in moderate to good yield. Finally, a rational mechanism was proposed.
- Zhou, Chao,Diao, Pinhui,Li, Xiaoji,Ge, Yanqin,Guo, Cheng
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supporting information
p. 371 - 374
(2018/06/27)
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- Copper-catalysed synthesis of alkylidene 2-pyrrolinone derivatives from the combination of α-keto amides and alkynes
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A Cu(i)-catalysed addition and cyclisation sequence has been developed for the synthesis of (E)-alkylidene pyrrolinone derivatives. The reactions incorporate simple α-keto amides and alkynes as substrates, and employ a commercially available Cu(i) catalyst. The process tolerates good variation of both starting materials, and delivers the desired pyrrolinones in good yields, with high levels of stereocontrol.
- Tan, Qian Wen,Chovatia, Praful,Willis, Michael C.
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supporting information
p. 7797 - 7800
(2018/11/21)
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- Friedel-Crafts Hydroxyalkylation of Indoles with α-Keto Amides using Reusable K3PO4/ nBu4NBr Catalytic System in Water
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A mild and operationally simple Friedel-Crafts hydroxyalkylation of indoles with α-keto amides was developed for the first time by using catalytic amount of K3PO4 and nBu4NBr in water as solvent through a solid-liquid inte
- Muthukumar, Alagesan,Sekar, Govindasamy
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p. 8827 - 8839
(2018/08/03)
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- CuCl/TMEDA/nor-AZADO-catalyzed aerobic oxidative acylation of amides with alcohols to produce imides
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Although aerobic oxidative acylation of amides with alcohols would be a good complement to classical synthetic methods for imides (e.g., acylation of amides with activated forms of carboxylic acids), to date, there have been no reports on oxidative acylation to produce imides. In this study, we successfully developed, for the first time, an efficient method for the synthesis of imides through aerobic oxidative acylation of amides with alcohols by employing a CuCl/TMEDA/nor-AZADO catalyst system (TMEDA = teramethylethylendiamine; nor-AZADO = 9-azanoradamantane N-oxyl). The proposed acylation proceeds through the following sequential reactions: aerobic oxidation of alcohols to aldehydes, nucleophilic addition of amides to the aldehydes to form hemiamidal intermediates, and aerobic oxidation of the hemiamidal intermediates to give the corresponding imides. This catalytic system utilizes O2 as the terminal oxidant and produces water as the sole by-product. An important point for realizing this efficient acylation system is the utilization of a TMEDA ligand, which, to the best of our knowledge, has not been employed in previously reported Cu/ligand/N-oxyl systems. Based on experimental evidence, we consider that plausible roles of TMEDA involve the promotion of both hemiamidal oxidation and regeneration of an active CuII-OH species from a CuI species. Here promotion of hemiamidal oxidation is particularly important. Employing the proposed system, various types of structurally diverse imides could be synthesized from various combinations of alcohols and amides, and gram-scale acylation was also successful. In addition, the proposed system was further applicable to the synthesis of α-ketocarbonyl compounds (i.e., α-ketoimides, α-ketoamides, and α-ketoesters) from 1,2-diols and nucleophiles (i.e., amides, amines, and alcohols).
- Kataoka, Kengo,Wachi, Keiju,Jin, Xiongjie,Suzuki, Kosuke,Sasano, Yusuke,Iwabuchi, Yoshiharu,Hasegawa, Jun-Ya,Mizuno, Noritaka,Yamaguchi, Kazuya
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p. 4756 - 4768
(2018/06/07)
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- Divergent Reactivity of gem-Difluoro-enolates toward Nitrogen Electrophiles: Unorthodox Nitroso Aldol Reaction for Rapid Synthesis of α-Ketoamides
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An amination reaction of in situ generated gem-difluoro-enolates has been explored with electrophilic nitrogen sources. While their exposure to azodicarboxylates smoothly produced fluorinated α-amino ketones, reaction with nitrosoarenes (nitroso aldol rea
- Reddy, Mallu Kesava,Ramakrishna, Isai,Baidya, Mahiuddin
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p. 4610 - 4613
(2018/08/07)
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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
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p. 546 - 551
(2017/01/16)
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- A Mild and Chemoselective Hydrosilylation of α-Keto Amides by Using a Cs2CO3/PMHS/2-MeTHF System
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A Cs2CO3-catalyzed hydrosilylation reaction of α-keto amides that proceeds through the in situ formation of MeSiH3 has been developed by using inexpensive polymethylhydrosiloxane in 2-methyltetrahydrofuran (2-MeTHF) as the solvent. A wide range of aryl and alkyl α-keto amides, prepared from anilines and alkylamines, were subjected to the hydrosilylation conditions to afford α-hydroxy amides in moderate to excellent yields. This transition-metal-free protocol was applied to a chemoselective hydrosilylation, in which reduction occurred at the carbonyl of the α-keto amide functionality over that of the simple ketone, and further extended to a gram-scale protocol.
- Kumar, Govindharaj,Muthukumar, Alagesan,Sekar, Govindasamy
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p. 4883 - 4890
(2017/09/13)
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- Hypervalent Iodine(III)-Promoted Phenyl Transfer Reaction from Phenyl Hydrazides to Nitriles
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A useful transformation of nitriles to N-phenyl amides has been achieved through a novel intermolecular phenyl transfer reaction from phenyl hydrazides and N-addition to nitriles in the presence of PIFA under mild and solvent-free conditions. This cross-coupling reaction includes the oxidative cleavage of sp2 C-N bonds of phenyl hydrazides to form a phenyl radical and the subsequent N-addition to cyanos to form new sp2 C-N bonds and provides efficient access to various N-phenyl amides in moderate to good yields under mild reaction conditions.
- Yan, Yan,Zhang, Zhiguo,Wan, Yameng,Zhang, Guisheng,Ma, Nana,Liu, Qingfeng
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supporting information
p. 7957 - 7963
(2017/08/14)
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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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- Potassium Phosphate-Catalyzed Chemoselective Reduction of α-Keto Amides: Route to Synthesize Passerini Adducts and 3-Phenyloxindoles
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A chemoselective reduction of α-keto amides to biologically important α-hydroxy amides (mandelamides) by polymethylhydrosiloxane (PMHS) using 5 mol% potassium phosphate (K3PO4) as catalyst has been developed. This transition metal-free protocol discloses excellent chemoselectivity for the ketone reduction of α-keto amides in the presence of other reducible functionalities like ketone, nitro, halides, nitrile and amide. Also, the chemoselectively reduced α-hydroxy amide has been derivatized to isocyanide-free Passerini adducts. The N-alkyl-α-hydroxy amides have been successfully converted to 3-phenyloxindole derivatives by treatment with methanesulfonyl cholride and triethylamine.
- Muthukumar, Alagesan,Mamillapalli, N. Chary,Sekar, Govindasamy
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p. 643 - 652
(2016/02/27)
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- Generation of Oxazolidine-2,4-diones Bearing Sulfur-Substituted Quaternary Carbon Atoms by Oxothiolation/Cyclization of Ynamides
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A novel method for metal-free oxothiolation of ynamides to construct oxazolidine-2,4-diones bearing sulfur-substituted quaternary carbon atoms has been developed. It represents a rare C-O bond cleavage of ynamides, as well as a facile and tandem approach for the formation of C-O, C-S, and C-Cl bonds. This redox-neutral protocol can be applied to the synthesis of multisubstituted oxazolidine-2,4-diones with good chemoselectivity and good yields of isolated products under mild conditions.
- Huang, Hai,Fan, Junzhen,He, Guangke,Yang, Zhimin,Jin, Xiaodong,Liu, Qi,Zhu, Hongjun
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p. 2532 - 2538
(2016/02/12)
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- Copper-catalyzed, hypervalent iodine mediated C=C bond activation of enaminones for the synthesis of α-keto amides
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An unprecedented C=C bond cleavage of enaminones has been realized by means of copper catalysis in the presence of hypervalent iodine (PhI(OAc)2). The cascade transformation based on this bond cleavage leads to the synthesis of various α-keto amides. Isotope labeling experiments suggest that water has acted as a source of oxygen atoms during the generation of the new carbonyl group.
- Wan, Jie-Ping,Lin, Yunfang,Cao, Xiaoji,Liu, Yunyun,Wei, Li
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supporting information
p. 1270 - 1273
(2016/01/15)
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- Enantioselective Construction of 3-Hydroxypiperidine Scaffolds by Sequential Action of Light and Rhodium upon N-Allylglyoxylamides
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3-Hydroxypiperidine scaffolds were enantioselectively constructed in an atom-economical way by sequential action of light and rhodium upon N-allylglyoxylamides. In a formal sense, the allylic C-H bond was selectively cleaved and enantioselectively added a
- Ishida, Naoki,Ne?as, David,Masuda, Yusuke,Murakami, Masahiro
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p. 7418 - 7421
(2015/06/30)
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- Enantioselective Synthesis of α-Hydroxy Amides and β-Amino Alcohols from α-Keto Amides
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Synthesis of enantiomerically enriched α-hydroxy amides and β-amino alcohols has been accomplished by enantioselective reduction of α-keto amides with hydrosilanes. A series of α-keto amides were reduced in the presence of chiral CuII/(S)-DTBM-SEGPHOS catalyst to give the corresponding optically active α-hydroxy amides with excellent enantioselectivities by using (EtO)3SiH as a reducing agent. Furthermore, a one-pot complete reduction of both ketone and amide groups of α-keto amides has been achieved using the same chiral copper catalyst followed by tetra-n-butylammonium fluoride (TBAF) catalyst in presence of (EtO)3SiH to afford the corresponding chiral β-amino alcohol derivatives.
- Mamillapalli, N. Chary,Sekar, Govindasamy
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supporting information
p. 18584 - 18588
(2016/01/25)
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- α-Carbonylimine to α-Carbonylamide: An efficient oxidative amidation approach
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Abstract Our interest in generating amide bonds by employing the activated C=N system has led to the development of an efficient oxidative amidation reaction between 2-oxoaldehyde and weak nucleophilic amines (anilines, benzamides and sulfonamides). Mechanistic studies support the involvement of α-carbonylimine (-CO-C=N-) based compounds or intermediates as a central feature of the reaction, in which an adjacent CO moiety enhances the electrophilicity of the C=N system, which favors attack of the oxidant (TBHP or SeO2), thereby resulting in the generation of the desired products in good yields. The direct oxidative coupling of 2-oxoaldehydes and weak nucleophilic amines has been accomplished through either MgSO4-TBHP-pyridine/CuBr, or SeO2·pyridine promoted methods. In the current study, SeO2·pyridine emerged as a versatile reagent with which to promote initial α-carbonylimine formation between 2-oxoaldehyde and weak nucleophilic amine, and subsequent oxidation to the corresponding α-carbonylamide. The reported methodology constitutes one of the few reports of the synthesis of α-ketoamides from anilines, perhaps the second report for the generation of α-ketoimides, and the first report of the generation of 2-oxoamides with sulfonamides.
- Padala, Anil K.,Mupparapu, Nagaraju,Singh, Deepika,Vishwakarma, Ram A.,Ahmed, Qazi Naveed
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supporting information
p. 3577 - 3586
(2015/06/08)
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- Visible-light initiated copper(i)-catalysed oxidative C-N coupling of anilines with terminal alkynes: One-step synthesis of α-ketoamides
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Development of C-N coupling processes is fundamentally important and challenging for the synthesis of biologically active molecules and drugs. Herein, we report a highly atom efficient green process for the synthesis of α-ketoamides via visible-light induced copper(i) chloride catalysed direct oxidative Csp-N coupling reactions using commercially available alkynes and anilines at room temperature without the use of hazardous chemicals and harsh reaction conditions. Forty-seven examples are presented using a broad range of substrates including electron deficient anilines and various terminal alkynes. The current photochemical process is able to achieve epoxide hydrolase inhibitors in one step with high yield (92-95%). This transformation is highly efficient and highly selective for the synthesis of α-ketoamides. This journal is
- Sagadevan, Arunachalam,Ragupathi, Ayyakkannu,Lin, Chun-Cheng,Hwu, Jih Ru,Hwang, Kuo Chu
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supporting information
p. 1113 - 1119
(2015/03/04)
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- Chemoselective Reductive Deoxygenation and Reduction of α-Keto Amides by using a Palladium Catalyst
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A palladium catalyst is used to synthesize 2,N-diphenylacetamides and α-hydroxy amides from readily available α-keto amides by chemoselective reductive deoxygenation and chemoselective reduction using polymethylhydrosiloxane (PMHS). This methodology has t
- Mamillapalli, N. Chary,Sekar, Govindasamy
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p. 3273 - 3283
(2015/11/03)
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- Cationic Ir/Me-BIPAM-catalyzed asymmetric intramolecular direct hydroarylation of α-ketoamides
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Asymmetric intramolecular direct hydroarylation of α-ketoamides gives various types of optically active 3-substituted 3-hydroxy-2-oxindoles in high yields with complete regioselectivity and high enantioselectivities (84-98 % ee). This is realized by the use of the cationic iridium complex [Ir(cod) 2](BArF4) and the chiral O-linked bidentate phosphoramidite (R,R)-Me-BIPAM. Carbon's got a brand new bond: Asymmetric intramolecular direct hydroarylation of α-ketoamides gives various optically active 3-substituted 3-hydroxy-2-oxindoles in high yields with complete regioselectivity and high enantioselectivities. This is realized by the use of an asymmetric cationic iridium complex formed in situ (see Scheme).
- Shirai, Tomohiko,Ito, Hajime,Yamamoto, Yasunori
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p. 2658 - 2661
(2014/03/21)
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- Organocatalytic asymmetric synthesis of functionalized 1,3,5- triarylpyrrolidin-2-ones via an aza-Michael/aldol domino reaction
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The organocatalytic asymmetric synthesis of functionalized 1,3,5-triarylpyrrolidin-2-ones bearing three contiguous stereocenters through an aza-Michael/aldol domino reaction of α-ketoamides with α,β-unsaturated aldehydes is described. The domino products
- Joie, Celine,Deckers, Kristina,Enders, Dieter
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p. 799 - 808
(2014/04/03)
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- A new class of tunable dendritic diphosphine ligands: Synthesis and applications in the Ru-catalyzed asymmetric hydrogenation of functionalized ketones
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A series of tunable G0-G3 dendritic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) ligands was prepared by attaching polyaryl ether dendrons onto the four phenyl rings on the P atoms. Their ruthenium complexes were employed in the asymmetric hydrogenation of β-ketoesters, α-ketoesters, and α-ketoamides to reveal the effects of dendron size on the catalytic properties. The second- and third-generation catalysts exhibited excellent enantioselectivities, which are remarkably higher than those obtained from the small molecular catalysts and the first-generation catalyst. Molecular modeling indicates that the incorporation of bulky dendritic wedges can influence the steric environments around the metal center. In addition, the ruthenium catalyst bearing a second-generation dendritic ligand could be recycled and reused seven times without any obvious decrease in enantioselectivity.
- Ma, Baode,Miao, Tingting,Sun, Yihua,He, Yanmei,Liu, Ji,Feng, Yu,Chen, Hui,Fan, Qing-Hua
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p. 9969 - 9978
(2014/08/18)
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- Metal free chemoselective reduction of α-keto amides using TBAF as catalyst
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The metal and ligand free chemoselective reduction of the keto group and complete reduction of the both keto and amide groups of α-keto amide with hydrosilanes using tetrabutylammoniumflouride (TBAF) as catalyst have been accomplished. This methodology affords an efficient and economic route for the synthesis of biologically important α-hydroxy amides and β-amino alcohols. The other important advantage of this TBAF catalyst is chemoselective reduction of ketones to corresponding alcohols in the presence of several other sensitive functional groups.
- Mamillapalli, N. Chary,Sekar, Govindasamy
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p. 61077 - 61085
(2015/02/19)
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- Iodine-mediated oxidation of ynamides: A facile access to N-monosubstituted α-ketoamides and α-ketoimides
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An efficient iodine-mediated oxidation reaction for ynamides has been developed to produce N-monosubstituted α-ketoamides and α-ketoimides. This oxidative method, which exhibits good functional group tolerance, was performed under mild conditions without a metal catalyst.
- Huang, Hai,He, Guangke,Zhu, Xiaolin,Jin, Xiaodong,Qiu, Shineng,Zhu, Hongjun
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p. 7174 - 7183
(2015/01/16)
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- A general metal free approach to α-ketoamides via oxidative amidation-diketonization of terminal alkynes
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A novel catalytic system TMSOTf/I2/DMSO for the oxidative coupling of terminal alkynes with virtually any primary/secondary amine leading to α-ketoamides has been developed. The reaction possibly proceeds via iminium ion formation, wherein DMSO acts as a solvent as well as an oxidizing agent. This journal is the Partner Organisations 2014.
- Deshidi, Ramesh,Kumar, Manjeet,Devari, Shekaraiah,Shah, Bhahwal Ali
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supporting information
p. 9533 - 9535
(2014/08/18)
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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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- Phosphine-free, efficient double carbonylation of aryl iodides with amines catalyzed by water-insoluble and water-soluble N-heterocyclic carbene-amine palladium complexes
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The water-insoluble and water-soluble N-heterocyclic carbene (NHC)-amine palladium complexes, Ipr-Pd(deba)Cl and SO3-Ipr-Pd(deba)Cl, were synthesized. Both catalysts exhibit excellent activity in the phosphine-free double carbonylation of aryl iodides with amines to produce α-keto amides. Moreover, as the water-soluble catalyst exhibits significant compatibility in the aqueous phase with the activities of different Pd-NHC complexes, we conclude that the intramolecular amine ligand strongly affects the selectivity of the products in double carbonylation reaction and serves as an alternative of phosphine ligands.
- Wang, Yan,Yang, Xiaolong,Zhang, Chunyan,Yu, Jianqiang,Liu, Jianhua,Xia, Chungu
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p. 2539 - 2546
(2014/09/29)
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- A simple, efficient, regioselective and one-pot preparation of N-hydroxy- and N-O-protected hydroxyindoles via cycloaddition of nitrosoarenes with alkynes. Synthetic scope, applications and novel by-products
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The thermal reaction between nitrosoarenes and alkynes under alkylating conditions produces N-alkoxyindoles as the major products in moderate to good yields and excellent regioselectivity. Various electrophiles are used affording different N-O-protected hydroxyindoles in a multi-component fashion. Privileged acetylenic substrates used in reactions with substituted nitrosoarenes are arylalkynes or propiolates. Potentially bioactive compounds and other classes of highly functionalizable indole products were prepared. Reactions between o-carbomethoxy-nitrosoarenes and arylacetylenes provided tricyclic compounds containing an acylaziridine indoline skeleton.
- Ieronimo, Gabriella,Mondelli, Alessandro,Tibiletti, Francesco,Maspero, Angelo,Palmisano, Giovanni,Galli, Simona,Tollari, Stefano,Masciocchi, Norberto,Nicholas, Kenneth M.,Tagliapietra, Silvia,Cravotto, Giancarlo,Penoni, Andrea
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p. 10906 - 10920
(2014/01/06)
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- A novel approach for the one-pot preparation of α-ketoamides by anodic oxidation
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The direct oxidative synthesis of α-ketoamides via anodic oxidation was developed by using dioxygen as a reactant under mild conditions. This methodology has a broad substrate scope (aromatic amines, aliphatic amines and ammonium acetate) and opens up an interesting and attractive avenue for the synthesis of α-ketoamide derivatives.
- Zhang, Zhenlei,Su, Jihu,Zha, Zhenggen,Wang, Zhiyong
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supporting information
p. 8982 - 8984
(2013/09/24)
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- A straightforward synthesis of N-monosubstituted α-keto amides via aerobic benzylic oxidation of amides
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An efficient sodium bicarbonate promoted aerobic oxidation reaction to prepare N-monosubstituted α-keto amides in the presence of n-tetrabutylammonium hydrogensulfate (TBAHS) was described. This reaction provides a very simple and convenient synthetic route to N-monosubstituted α-keto amides from easily available aryl- or heteroarylacetamides in good to high yields without using toxic reagents and harsh conditions.
- Shao, Jun,Huang, Xiaomei,Wang, Siyuan,Liu, Bingxin,Xu, Bin
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p. 573 - 579
(2012/01/13)
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- Biocatalytic reduction of α-keto amides to (R)-α-hydroxy amides using Candida parapsilosis ATCC 7330
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Biocatalytic reduction of primary and secondary α-keto amides was accomplished using whole cells of Candida parapsilosis ATCC 7330. The primary (R)-α-hydroxy amides were obtained in good enantiomeric excess (up to 94%) and conversion (88-99%) as compared to the secondary (R)-α-hydroxy amides.
- Stella, Selvaraj,Chadha, Anju
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p. 345 - 352
(2013/01/15)
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- Simplified procedure for TEMPO-catalyzed oxidation: Selective oxidation of alcohols, α-hydroxy esters, and amides using TEMPO and calcium hypochlorite
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A wide range of primary and secondary multifunctional alcohols, α-hydroxyamides, and α-hydroxyesters were oxidized to their corresponding aldehydes, ketones, α-ketoamides, and α-ketoesters under mild reaction conditions using 2,2,6,6-tetramethylpiperidine-1-oxyl as a catalyst with calcium hypochlorite as an oxidant [TEMPO-Ca(OCl)2]. This simplified method does not require any transition metals, acids, or bases and demonstrates controlled and selective oxidation of structurally diverse alcohols, affording moderate to excellent yields at room temperature.
- Reddy, Sabbasani Rajasekhara,Stella, Selvaraj,Chadha, Anju
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experimental part
p. 3493 - 3503
(2012/09/22)
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- Synthesis of N -arylisatins by the reaction of arynes with methyl 2-Oxo-2-(arylamino)acetates
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N-Arylisatins are efficiently prepared by the reaction of 2-oxo-2-(arylamino)acetates and arynes under mild reaction conditions
- Rogness, Donald C.,Larock, Richard C.
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experimental part
p. 4980 - 4986
(2011/08/06)
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- Nickel-catalyzed intramolecular nucleophilic addition of aryl or vinyl chlorides to α-ketoamides through C-Cl bond activation
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Nickeleophilic addition! The first example of a nickel-catalyzed direct intramolecular nucleophilic addition of aryl or vinyl chlorides to α-ketoamides through C-Cl bond activation is reported, which takes place under mild reaction conditions (see scheme).
- Hu, Jin-Xiu,Wu, Hao,Li, Chuan-Ying,Sheng, Wei-Jian,Jia, Yi-Xia,Gao, Jian-Rong
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supporting information; experimental part
p. 5234 - 5237
(2011/07/07)
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- Dioxygen activation under ambient conditions: Cu-catalyzed oxidative amidation-diketonization of terminal alkynes leading to α-ketoamides
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(Figure Presented) A novel Cu-catalyzed oxidative amidation-diketonization reaction of terminal alkynes leading to α-ketoamides has been developed. This chemistry offers a valuable mechanistic insight into this novel Cu catalysis via a radical process. O2 not only participates as the ideal oxidant but also undergoes dioxygen activation under ambient conditions in this transformation.
- Chun, Zhang,Ning, Jiao
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supporting information; experimental part
p. 28 - 29
(2010/03/25)
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- Superacid-promoted reactions of α-ketoamides and related systems
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(Chemical Equation Presented) The superacid-promoted reactions of α-hydroxy and α-ketoamides have been studied. Ionization of these compounds leads to varied aryl-substituted oxyindole products. In some cases, electrocyclization can lead to substituted fl
- Sai, Kiran Kumar Solingapuram,Esteves, Pierre M.,Da Penha, Eduardo Tanoue,Klumpp, Douglas A.
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p. 6506 - 6512
(2008/12/22)
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- Formation of acrylanilides, acrylamides, and amides directly from carboxylic acids using thionyl chloride in dimethylacetamide in the absence of bases
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A general one-pot procedure is described that rapidly converts acrylic acid to anilides upon sequential treatment of the acid in dimethylacetamide (DMAC) with thionyl chloride and stoichiometric amounts of anilines in 88-98% yields, with DMAC offering rate and stability advantages over the use of DMF. The use of DMAC was extended to other organic acids in forming anilides. Benzylamine amides can also be formed using stoichiometric amounts of benzylamine and brought to completion by warming in the absence of additional base. In addition, it was shown that tert-butylamides can be easily formed with the addition of excess tert-butylamine at 20 °C.
- Cvetovich, Raymond J.,DiMichele, Lisa
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p. 944 - 946
(2012/12/23)
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- Unprecedented 1,3-dipolar cycloaddition of azomethine ylides to ester carbonyl
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Fluorinated azomethine ylides generated by the reaction of difluorocarbene with aryl and alkyl imines of O-acylated salicylaldehyde undergo intramolecular 1,3-dipolar cycloaddition across the ester carbonyl to give 2,8-dioxa-6-azabicyclo[3.2.1]octane derivatives.
- Novikov, Mikhail S.,Voznyi, Igor V.,Khlebnikov, Alexander F.,Kopf, Juergen,Kostikov, Rafael R.
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p. 1628 - 1630
(2007/10/03)
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- One-Pot Synthesis of Unsymmetrical Ketones by the Reaction of Decacarbonyldimanganese with Two Kinds of Alkyllithiums
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Decacarbonyldimanganese (Mn2(CO)10) is utilized as a phosgene equivalent for the one-pot preparation of unsymmetrical ketones. By a successive treatment of Mn2(CO)10 with two kinds of alkyllithiums, unsymmetrical ketones are obtained in high selectivity. Unsymmetrical α-diketones are generated when the above reaction is carried out in the presence of trimethyl phosphite and is quenched with N-bromosuccinimide.
- Yamamoto, Hiroshi M.,Sakurai, Hidehiro,Narasaka, Koichi
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p. 157 - 161
(2007/10/03)
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