- Some Unusual Reaction of Weinreb Amides
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Certain N-methoxy-N-methyl amides yield products of formal reduction and/or rearrangement upon exposure to tert-butyldimethylsilyl triflate and collidine or triethylamine.
- Keck, Gary E.,McHardy, Stanton F.,Murry, Jerry A.
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- Assemblies of 1,4-Bis(diarylamino)naphthalenes and Aromatic Amphiphiles: Highly Reducing Photoredox Catalysis in Water
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Host-guest assemblies of a designed 1,4-bis(diarylamino)naphthalene and V-shaped aromatic amphiphiles consisting of two pentamethylbenzene moieties bridged by an m -phenylene unit bearing two hydrophilic side chains emerged as highly reducing photoredox catalysis systems in water. An efficient demethoxylative hydrogen transfer of Weinreb amides has been developed. The present supramolecular strategy permits facile tuning of visible-light photoredox catalysis in water.
- Abe, Manabu,Akita, Munetaka,Chitose, Youhei,Hyodo, Yuki,Koike, Takashi,Takahashi, Keigo,Yoshizawa, Michito
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- Direct synthesis of amides from nonactivated carboxylic acids using urea as nitrogen source and Mg(NO3)2or imidazole as catalysts
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A new method for the direct synthesis of primary and secondary amides from carboxylic acids is described using Mg(NO3)2·6H2O or imidazole as a low-cost and readily available catalyst, and urea as a stable, and easy to manipulate nitrogen source. This methodology is particularly useful for the direct synthesis of primary and methyl amides avoiding the use of ammonia and methylamine gas which can be tedious to manipulate. Furthermore, the transformation does not require the employment of coupling or activating agents which are commonly required.
- Blacker, A. John,Chhatwal, A. Rosie,Lomax, Helen V.,Marcé, Patricia,Williams, Jonathan M. J.
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p. 5808 - 5818
(2020/06/21)
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- Rh(III)-Catalyzed Distal C-H Alkenylation of Weakly Coordinating Acetamides Via Desilylation Pathway
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Rh(III)-Catalyzed distal ortho-C?H alkenylation of arylacetamides have been reported employing acetamide, a weak coordinating group, as a directing group. This challenging C?H alkenylation of arylacetamides has been achieved by using arylalkynyl silanes as a surrogate for terminal alkynes under redox neutral process through desilylation pathway. The control experiments suggest that the in situ generatedRh-species is likely to be Lewis acidic, which is playing a vital role in the desilylation step. (Figure presented.).
- Ramesh, Vinay Bapu,Muniraj, Nachimuthu,Prabhu, Kandikere Ramaiah
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supporting information
p. 3683 - 3688
(2019/07/12)
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- Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
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Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.
- Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
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p. 11823 - 11838
(2019/10/02)
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- Ruthenium-Catalyzed Oxidative Amidation of Alkynes to Amides
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Complex CpRuCl(PPh3)2 catalyzes reactions of terminal alkynes with 4-picoline N-oxide and primary and secondary amines to afford the corresponding amides. The reactions occur in chlorinated solvent and aqueous medium, showing applications in peptide chemistry. Stoichiometric studies reveal that the true catalysts of the processes are the vinylidene cations [CpRu(=C=CHR)(PPh3)2]+ which are oxidized to the Ru(η2-CO)-ketenes by the N-oxide. Finally, nucleophilic additions of primary and secondary amines to the free ketenes yield the corresponding amides.
- álvarez-Pérez, Andrea,Esteruelas, Miguel A.,Izquierdo, Susana,Varela, Jesús A.,Saá, Carlos
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supporting information
p. 5346 - 5350
(2019/07/08)
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- CRBN LIGANDS AND USES THEREOF
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The present invention provides compounds, compositions thereof, and methods of using the same for the inhibition of CRBN, and the treatment of CRBN-mediated disorders.
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Paragraph 00572-00574
(2019/08/20)
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- Selective α-Oxyamination and Hydroxylation of Aliphatic Amides
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Compared to the α-functionalization of aldehydes, ketones, even esters, the direct α-modification of amides is still a challenge because of the low acidity of α-CH groups. The α-functionalization of N?H (primary and secondary) amides, containing both an unactived α-C?H bond and a competitively active N?H bond, remains elusive. Shown herein is the general and efficient oxidative α-oxyamination and hydroxylation of aliphatic amides including secondary N?H amides. This transition-metal-free chemistry with high chemoselectivity provides an efficient approach to α-hydroxy amides. This oxidative protocol significantly enables the selective functionalization of inert α-C?H bonds with the complete preservation of active N?H bond.
- Li, Xinwei,Lin, Fengguirong,Huang, Kaimeng,Wei, Jialiang,Li, Xinyao,Wang, Xiaoyang,Geng, Xiaoyu,Jiao, Ning
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supporting information
p. 12307 - 12311
(2017/09/11)
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- Synthesis of aryl anilinomaleimide based derivatives as glycogen synthase kinase-3β inhibitors with potential role as antidepressant agents
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A series of aryl anilinomaleimide based derivatives has been synthesized and evaluated for in vitro glycogen synthase kinase-3β (GSK-3β) inhibitory activity. A large number of compounds from the series exhibited moderate to potent inhibitory activity against GSK-3β, with more than one-third of the compounds showing inhibition with IC50 values 50 values of 0.09, 0.12, 0.17, 0.19, 0.21 and 0.23 μM respectively), were further investigated for antidepressant activity by the widely accepted forced swim test and tail suspension test (FST and TST) models. All the tested compounds displayed antidepressant-like effects, particularly compounds 8j and 8b, which exhibited significant antidepressant activity, about 1.4-fold higher than fluoxetine, a standard antidepressant drug in both FST and TST. Preliminary structure-activity relationships have also been generated based on the experimental data obtained.
- Tantray, Mushtaq A.,Khan, Imran,Hamid, Hinna,Alam, Mohammad Sarwar,Dhulap, Abhijeet,Kalam, Abul
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p. 6109 - 6119
(2016/07/16)
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- Carboxyl activation of 2-mercapto-4,6-dimethylpyrimidine through n-acyl-4,6-dimethylpyrimidine-2-thione: A chemical and spectrophotometric investigation
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2-Mercapto-4,6-dimethylpyrimidine, as effective carboxyl activating group, has been successfully proved by converting it into respective acyl derivatives and the subsequent conversion to the amides and esters respectively using amines, amino alcohols and alcohols. The aminolysis and esterification were monitored chemically and spectrophotometrically. This paved way to establish that the above mercaptopyrimidine derivative is an efficient carboxyl activating group applicable in solid phase peptide synthesis.
- Rajan
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p. 287 - 291
(2015/01/30)
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- α-Diazo-β-ketonitriles: Uniquely reactive substrates for arene and alkene cyclopropanation
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An investigation of the intramolecular cyclopropanation reactions of α-diazo-β-ketonitriles is reported. These studies reveal that α-diazo-β-ketonitriles exhibit unique reactivity in their ability to undergo arene cyclopropanation reactions; other similar acceptor-acceptor- substituted diazo substrates instead produce mixtures of C-H insertion and dimerization products. α-Diazo-β-ketonitriles also undergo highly efficient intramolecular cyclopropanation of tri- and tetrasubstituted alkenes. In addition, the α-cyano-α-ketocyclopropane products are demonstrated to serve as substrates for SN2, SN2′, and aldehyde cycloaddition reactions.
- Nani, Roger R.,Reisman, Sarah E.
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supporting information
p. 7304 - 7311
(2013/06/27)
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- Efficient synthesis of N-methylamides and amines via 4-(alkylamino)benzyl- N-methylamine as a new protecting group
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4-(Alkylamino)benzyl-N-methylamine is a good protecting group for the synthesis of N-methylamides and amines. The N-debenzylation of N-methylamides and amines can be carried out selectively and efficiently under condition using trifluoroacetic acid (TFA).
- Lee, Sang-Hak,Mu, Yu,Kim, Gun-Woo,Kim, Jin-Seok,Park, Seok-Hwi,Jin, Tian,Lee, Kee-Young,Ham, Won-Hun
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p. 1749 - 1764
(2013/09/12)
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- Oxidative C-H homodimerization of phenylacetamides
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A range of secondary and tertiary phenylacetamides undergo oxidative homodimerization to afford biaryls. The reaction proceeds under palladium catalysis in the presence of a copper cocatalyst and oxygen and is most effective for electron-rich substrates.
- Pintori, Didier G.,Greaney, Michael F.
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supporting information; experimental part
p. 5713 - 5715
(2011/12/04)
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- COMPOUND WITH AGITATION EFFECT ON PEROXISOME PROLIFERATOR-ACTIVATED RECEPTOR , AND PREPARATION METHOD AND USE THEREOF
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The present invention provides a novel compound of formula I, which has an agitation effect on the peroxisome proliferator-activated receptor subtype δ (PPARδ), to a pharmaceutical composition comprising the compound, to a process for preparation of the compound and to use of the compound in the manufacture of a medicament for treating or preventing a disease which could be treated or prevented by activating PPARδ thereof, said disease is one or more from the group comprising metabolic syndrome, obesity, dyslipidemia, pathoglycemia, insulin resistance, senile dementia and tumors. The present invention also relates to a new intermediate used in the preparation of the novel compound and a process for preparation of the intermediate.
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Page/Page column 24
(2011/06/24)
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- COMPOUND WITH AGITATION EFFECT ON PEROXISOME PROLIFERATOR-ACTIVATED RECEPTOR. PROCESS FOR ITS PREPARATION AND USE THEREOF
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The present invention provides a novel compound of formula I, which has an agitation effect on the peroxisome proliferator-activated receptor subtype δ (PPARδ), to a pharmaceutical composition comprising the compound, to a process for preparation of the compound and to use of the compound in the manufacture of a medicament for treating or preventing a disease which could be treated or prevented by activating PPARδ thereof, said disease is one or more from the group comprising metabolic syndrome, obesity, dyslipidemia, pathoglycemia, insulin resistance, senile dementia and tumors. The present invention also relates to a new intermediate used in the preparation of the novel compound and a process for preparation of the intermediate.
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Page/Page column 16
(2012/01/13)
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- Process development and pilot-scale synthesis of new cyclization conditions of substituted phenylacetamides to tetrahydroisoquinoline-2-ones using Eaton's reagent
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Tetrahydroisoquinoline is a ubiquitous structural framework presented in numerous pharmacologically relevant molecules. Although accessible by the Pictet-Spengler cyclization, conditions commonly used for such cyclizations are often difficult to implement on scale. Herein, we report the development of a scaleable approach utilizing Eaton's reagent for the cyclization of substituted phenylacetamide analogues to tetrahydroisoquinoline-2-one. The development, optimization, and safety hazard evaluations, which outline the benefits and ease of workup of this new process, are discussed.
- Ulysse, Luckner G.,Yang, Qiang,McLaws, Mark D.,Keefe, Daniel K.,Guzzo, Peter R.,Haney, Brian P.
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experimental part
p. 225 - 228
(2010/04/29)
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- A simple and highly efficient one-pot procedure for the synthesis of amides via beckmann rearrangements using 1-tosylimidazole (TsIm)
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A facile and highly efficient method for one-pot Beckmann rearrangement of ketoximes into N-substituted amides using N-(p-toluenesulfonyl)imidazole (TsIm) is described. In this method, ketoximes are refluxed with TsIm and Cs2CO3 in the presence of SiO2 as a recyclable catalyst in DMF affording the corresponding amides in high yields. This methodology is highly efficient and regioselective for various structurally diverse ketoximes including symmetrical and unsymmetrical as well as cyclic oximes. The results of quantum mechanical studies used to rationalize the experimental outcomes are discussed. Copyright Taylor & Francis Group, LLC.
- Rad, Mohammad Navid Soltani,Khalafi-Nezhad, Ali,Behrouz, Somayeh,Amini, Zohreh,Behrouz, Marzieh
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experimental part
p. 1658 - 1671
(2010/09/09)
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- Metal-free reductive cleavage of N-O bonds in weinreb amides by an organic neutral super-electron donor
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The scope of neutral organic super-electron donors as reducing agents has been extended to include the reductive cleavage of N-O bonds in Weinreb amides. This methodology proved to be applicable to a large array of substrates to afford their reduced counterparts in good to excellent yields. The variation in reactivity within the set of tested amides is rationalised. Georg Thieme Verlag Stuttgart.
- Cutulic, Sylvain P. Y.,Murphy, John A.,Farwaha, Hardeep,Zhou, Sheng-Ze,Chrystal, Ewan
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experimental part
p. 2132 - 2136
(2009/04/08)
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- P2O5/SiO2-catalyzed one-pot synthesis of amides from ketones via schmidt reaction under microwave irradiation in dry media
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A facile and efficient method for the preparation of amides from ketones by the Schmidt reaction is described for the first time using P 2 O 5 /SiO 2 and sodium azide under solvent-free microwave irradiation. Advantages of this procedure are selectivity, good yields, a simple operation, short reaction time, and solvent-free conditions. Copyright Taylor & Francis Group, LLC.
- Eshghi, Hossein,Hassankhani, Asadollah
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p. 2211 - 2216
(2007/10/03)
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- Silica sulfuric acid as a reusable catalyst for the conversion of ketones into amides by a Schmidt reaction under solvent-free conditions
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Silica sulfuric acid is a highly efficient reagent for the conversion of a variety of ketones into the corresponding amides by a Schmidt reaction under solvent-free conditions. Cyclic, aliphatic and aromatic ketones with electron-donating or withdrawing substituents may be converted easily in excellent yield. The major advantages of this method are: operational simplicity, the ready availability of the reagent, selectivity, general applicability, mild reaction conditions, short reaction times and high yields. The recovered catalyst could be used in new attempts without any purification.
- Eshghi, Hossein,Hassankhani, Asadollah,Mosaddegh, Elaheh
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p. 218 - 219
(2007/10/03)
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- An easy method for the generation of amides from ketones by a Beckmann type rearrangement mediated by microwave
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A facile and efficient procedure is developed for one-pot synthesis of amides from ketones in the presence of P2O5/SiO 2 reagent in dry media under microwave irradiation. Ketoximes indirectly in the same conditions gave amides by Beckmann rearrangement.
- Eshghi, Hossein,Gordi, Zinat
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p. 2971 - 2978
(2007/10/03)
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- Helper inducers for differentiation therapy and chemoprevention of cancer
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Cancer cells are blocked from entering differentiation pathways because of abnormal methylation enzymes, which are responsible for keeping cancer cells in cycling state. Effective differentiation inducers are those capable of acting directly or indirectly to convert abnormal methylation enzymes into normal enzymes, thereby enabling cancer cells to undergo terminal differentiation. Differentiation employing inducer alone often can not reach completion because of the damage created by the inducer. Such damage can be prevented if differentiation is induced in the presence of helper inducers, which are basically inhibitors of the component enzymes of methylation. Thus, differentiation induced in the presence of helper inducers is more likely to reach completion. Therefore, helper inducers are essential components of differentiation therapy, not just merely to potentiate the activity of differentiation inducers. The present inventors discover that alkyl phenylacetamides, alkyl phenylacetate, 2,4-dichlorophenylacetate, and indole acetate are potent helper inducers.
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- AN ALTERNATIVE PROCEDURE FOR THE ALUMINUM-MEDIATED CONVERSION OF ESTERS TO AMIDES
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A convenient method has been developed for directly converting esters to amides using reagents derived from the reaction of trimethylaluminum with ammonium chloride, methylamine hydrochloride or dimethylamine hydrochloride.
- Levin, Jeremy I.,Turos, Edward,Weinreb, Steven M.
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p. 989 - 994
(2007/10/02)
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