- Direct Amidation of Esters by Ball Milling**
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The direct mechanochemical amidation of esters by ball milling is described. The operationally simple procedure requires an ester, an amine, and substoichiometric KOtBu and was used to prepare a large and diverse library of 78 amide structures with modest to excellent efficiency. Heteroaromatic and heterocyclic components are specifically shown to be amenable to this mechanochemical protocol. This direct synthesis platform has been applied to the synthesis of active pharmaceutical ingredients (APIs) and agrochemicals as well as the gram-scale synthesis of an active pharmaceutical, all in the absence of a reaction solvent.
- Barreteau, Fabien,Battilocchio, Claudio,Browne, Duncan L.,Godineau, Edouard,Leitch, Jamie A.,Nicholson, William I.,Payne, Riley,Priestley, Ian
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supporting information
p. 21868 - 21874
(2021/09/02)
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- Method for preparing amide compound by photocatalysis of nitrogen-containing heterocyclic compound
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The invention provides a method for preparing an amide compound by photocatalysis of a nitrogen-containing heterocyclic compound. The method comprises the following steps: mixing the nitrogen-containing heterocyclic compound, organic carboxylic acid and tetrahalomethane in a solvent, adding a catalyst, and reacting under the illumination condition to prepare the amide compound. According to the invention, the organic carboxylic acid, the nitrogen-containing heterocyclic compound containing reactive hydrogen on nitrogen atoms and the tetrahalomethane are used as raw materials, so the raw materials are wide in source, low in cost and high in safety, and large-scale production is facilitated; the halogen simple substance is co-produced in the reaction process, the added value is high, a large amount of waste is prevented from being generated, and the method has high atom economy and environmental friendliness; light conditions are adopted to replace traditional heating and high-pressure conditions, the reaction conditions are mild, environmental pollution is reduced, and the reaction cost is reduced; the method has the advantages of good substrate applicability, mild process conditions, environmental protection, simple process, simple and feasible operation method, and facilitation of popularization and application.
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Paragraph 0067-0070; 0093; 0094
(2021/06/06)
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- Remarkably Efficient Iridium Catalysts for Directed C(sp2)-H and C(sp3)-H Borylation of Diverse Classes of Substrates
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Here we describe the discovery of a new class of C-H borylation catalysts and their use for regioselective C-H borylation of aromatic, heteroaromatic, and aliphatic systems. The new catalysts have Ir-C(thienyl) or Ir-C(furyl) anionic ligands instead of the diamine-type neutral chelating ligands used in the standard C-H borylation conditions. It is reported that the employment of these newly discovered catalysts show excellent reactivity and ortho-selectivity for diverse classes of aromatic substrates with high isolated yields. Moreover, the catalysts proved to be efficient for a wide number of aliphatic substrates for selective C(sp3)-H bond borylations. Heterocyclic molecules are selectively borylated using the inherently elevated reactivity of the C-H bonds. A number of late-stage C-H functionalization have been described using the same catalysts. Furthermore, we show that one of the catalysts could be used even in open air for the C(sp2)-H and C(sp3)-H borylations enabling the method more general. Preliminary mechanistic studies suggest that the active catalytic intermediate is the Ir(bis)boryl complex, and the attached ligand acts as bidentate ligand. Collectively, this study underlines the discovery of new class of C-H borylation catalysts that should find wide application in the context of C-H functionalization chemistry.
- Chattopadhyay, Buddhadeb,Hassan, Mirja Md Mahamudul,Hoque, Md Emdadul
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p. 5022 - 5037
(2021/05/04)
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- DECONSTRUCTIVE FUNCTIONALIZATION METHODS AND COMPOUNDS
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Disclosed herein, inter alia, are deconstructive functionalization methods and compounds made using the same.
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Paragraph 0435; 0450
(2020/01/31)
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- Copper-catalyzed aerobic oxidative C-C bond cleavage of simple ketones for the synthesis of amides
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A Cu-catalyzed oxidative amidation of simple ketones with amines via carbon-carbon (C-C) bond cleavage has been developed. A number of aryl and alkyl ketones could be easily converted to amides using cheap copper salt as the catalyst and O2 as the oxidant with a wide range of amines, including primary and secondary amines. This method shows a notable advantage of the broad scope for the substrate, thus providing a practical approach to amides. A plausible mechanism is proposed based on the preliminary experiments.
- Li, Ke,Liu, Wei,Liu, Yu-Feng,Yang, Guo-Ping,Zeng, Kai
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p. 6958 - 6964
(2020/10/02)
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- Synthesis method of amide compound
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The invention discloses a synthesis method of an amide compound. The synthesis method comprises the following step: carrying out a photocatalytic reaction on benzyl alcohol with a structure as shown in a formula (I) and an amine compound with a structure as shown in a formula (II) in the presence of photocatalyst-loaded metal P-C3N4 by using an organic solvent as a medium to obtain the amide compound with a structure as shown in a formula (III). The synthesis method does not need a heat source for heat supply, avoids high-temperature reaction, is simple to operate, short in reaction time and simple in aftertreatment, and can easily realize industrial production.
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Paragraph 0074; 0080-0082; 0092-0093
(2020/09/09)
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- Formal Deoxygenative Hydrogenation of Lactams Using PNHP-Pincer Ruthenium Complexes under Nonacidic Conditions
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A formal deoxygenative hydrogenation of amides to amines with RuCl2(NHC)(PNHP) (NHC = 1,3-dimethylimizadol-2-ylidene, PNHP = bis(2-diphenylphosphinoethyl)amine) is described. Various secondary amides, especially NH-lactams, are reduced with H2 (3.0-5.0 MPa) to amines at a temperature range of 120-150 °C with 1.0-2.0 mol % of PNHP-Ru catalysts in the presence of Cs2CO3. This process consists of (1) deaminative hydrogenation of secondary amides to generate primary amines and alcohols, (2) dehydrogenative coupling of the transient amines with alcohols to generate imines, and (3) hydrogenation of imines to give the formally deoxygenated secondary amine products.
- Ogata, Osamu,Nara, Hideki,Matsumura, Kazuhiko,Kayaki, Yoshihito
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p. 9954 - 9959
(2019/12/24)
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- Method for preparing amide compounds
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The invention discloses a method for preparing amide compounds. The method comprises the step of subjecting organic carboxylate with a structure represented by a formula (I) shown in the description and an amine compound with a structure represented by a formula (II) shown in the description to a grinding reaction, thereby preparing an amide compound with a structure represented by a formula (III)shown in the description and an alcohol compound with a structure represented by a formula (IV) shown in the description. According to the synthesis method, a heat source is not required to supply heat, an organic solvent is not required to serve as a medium, the operation is simple, the reaction time is short, the aftertreatment is simple, and thus, industrial production is easy to achieve.
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Paragraph 0091-0092
(2019/06/05)
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- Frustrated Lewis Pair Catalyzed Hydrogenation of Amides: Halides as Active Lewis Base in the Metal-Free Hydrogen Activation
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A method for the metal-free reduction of carboxylic amides using oxalyl chloride as an activating agent and hydrogen as the final reductant is introduced. The reaction proceeds via the hydrogen splitting by B(2,6-F2-C6H3)3 in combination with chloride as the Lewis base. Density functional theory calculations support the unprecedented role of halides as active Lewis base components in the frustrated Lewis pair mediated hydrogen activation. The reaction displays broad substrate scope for tertiary benzoic acid amides and α-branched carboxamides.
- Sitte, Nikolai A.,Bursch, Markus,Grimme, Stefan,Paradies, Jan
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supporting information
p. 159 - 162
(2019/01/04)
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- Amide Effects in C?H Activation: Noncovalent Interactions with L-Shaped Ligand for meta Borylation of Aromatic Amides
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A new concept for the meta-selective borylation of aromatic amides is described. It has been demonstrated that while esters gave para borylations, amides lead to meta borylations. For achieving high meta selectivity, an L-shaped bifunctional ligand has been employed and engages in an O???K noncovalent interaction with the oxygen atom of the moderately distorted amide carbonyl group. This interaction provides exceptional control for meta C?H activation/borylation.
- Bisht, Ranjana,Hoque, Md Emdadul,Chattopadhyay, Buddhadeb
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p. 15762 - 15766
(2018/11/10)
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- Product Control using Substrate Design: Ruthenium-Catalysed Oxidative C?H Olefinations of Cyclic Weinreb Amides
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A new class of Weinreb amides has been developed as directing groups for the ruthenium-catalysed regioselective oxidative C?H olefination. The new Weinreb amides successfully inhibit the N?O bond reductive cleavage usually associated with the cationic ruthenium system, thereby keeping intact the synthetic utility of Weinreb amides. Mechanistic studies reveal interesting aspects of the directing group capabilities of Weinreb amides when compared to simple amides of similar structures.
- Das, Riki,Kapur, Manmohan
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supporting information
p. 16986 - 16990
(2016/11/17)
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- Supported cobalt oxide nanoparticles as efficient catalyst in esterification and amidation reactions
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Co/SBA-15 nanoparticle catalysts (CoNP) were prepared using a commonly adapted synthetic route and then utilised for esterification and amidation reactions using aromatic and linear chain compounds for the production of long chain esters and amides. The study shows that the use of CoNP catalysts favours the use of aromatic reactants with electron donating substituents specifically in the para position. For the amidation reaction, good to excellent yields were obtained demonstrating tolerance towards differently substituted aromatic compounds. Overall, the synthesized catalysts proved to be efficient and highly versatile, and recyclable under the investigated conditions.
- Rajabi, Fatemeh,Raessi, Mojdeh,Arancon, Rick A.D.,Saidi, Mohammad Reza,Luque, Rafael
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p. 122 - 126
(2015/01/09)
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- Aerobic oxidative amidation of aromatic and cinnamic aldehydes with secondary amines by CuI/2-pyridonate catalytic system
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A simple and convenient CuI/2-pyridonate catalytic system for the oxidative amidation of aldehydes with secondary amines has been developed. With this system, a variety of useful arylamides have been synthesized in moderate to good yields in the presence of small amount of copper catalyst and the pyridonate ligand, generating only water as a coproduct. Synthesis of cinnamamides was also achieved by the reactions of cinnamaldehydes with secondary amines in moderate yields. Air was successfully employed as a green oxidant in this catalytic system, achieving a safe and atom-efficient system for the synthesis of amides.
- Zhu, Mingwen,Fujita, Ken-Ichi,Yamaguchi, Ryohei
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p. 9102 - 9109,8
(2012/12/11)
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- OXIDATION OF ORGANIC NITROGEN COMPOUNDS BY MEANS OF RUTHENIUM TETROXIDE: SELECTIVE PREPARATION OF N-SUBSTITUTED LACTAMS
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1-Formyl-, 1-acetyl-, and 1-benzoyl-perhydro-azepines and -azocines are oxidized by RuO4 to the corresponding N-acyllactams; the 1-benzyl analogues also undergo major endocyclic oxidation to 1-benzyllactams.
- Tangari, Nicola,Giovine, Maria,Morlacchi, Flaviano,Vetuschi, Claudio
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p. 325 - 328
(2007/10/02)
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- Palladium-Catalysed Double Carbonylation of Aryl Halides To Give α-Keto Amides. Mechanistic Studies
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Various aryl halides are catalytically converted into α-keto amides and amides on treatment with secondary amines and carbon monoxide.Palladium complexes containing tertiary phosphine ligands, particularly diphenylmethylphosphine and 1,4-bis(diphenylphosphino)butane, are most effective among other transition-metal complexes.Detailed examination of factors controlling the reaction rates and selectivity for α-keto amide formation revealed the following characteristics of the reactions. (a) Reactivity of phenyl halide decreases in the order PhI > PhBr >> PhCl. (b) Oxidative addition of phenyl bromide constitutes the rate-determining step in double carbonylation of phenyl bromide, whereas in the reaction of phenyl iodide the rate determinig step is associated with the reaction of a catalitically active palladium species with carbon monoxide. (c) Introduction of an electron-withdrawing substituent into the para position of phenyl halide enhances the reactivity but decreases the selectivity for α-keto amide. (d) Employment of amines of high basicity (pKb Et2NH > piperidine > hexamethyleneimine > Me2NH > pyrrolidine probably reflects the decrease in steric bulkiness of amines. (f) Although primary amines are in general not suitable for the double carbonylation, tert-butylamine can be used because of its inertness to the product α-keto amide.Reactivity of trans-PdPh(I)(PMePh2)2 and trans-Pd(COPh)I(PMePh2)2, supposed intermediates in the catalytic reaction of PhI, toward amines and CO was examined.The relative reactivity of six secondary amines with the benzoylpalladium complex increasing in the order Pr2NH Et2NH piperidine Me2NH hexamethyleneimine pyrrolidine was found to be inversely correlated with decreasing selectivity order for α-keto amide formation in the catalytic systems.On the basis of the experimental results, a mechanism consisting of two catalytic cycles to produce α-keto amides and amides has been proposed.
- Ozawa, Fumiyuki,Soyama, Hidehiko,Yanagihara, Hisayoshi,Aoyama, Issei,Takino, Hiroaki,et al.
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p. 3235 - 3245
(2007/10/02)
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