1485-70-7Relevant articles and documents
Highly selective amidation of benzylic alcohols with nitriles. A modified ritter reaction
Firouzabadi,Sardarian,Badparva
, p. 601 - 607 (1994)
Benzyl alcohols react selectively with different nitriles in the presence of a catalytic amount of boron trifluoride and produce amides in high yields. Deactivated p-nitrobenzyl, allylic, primary, secondary, and tertiary saturated alcohols do not react.
Rapid multiphase carbonylation reactions by using a microtube reactor: Applications in positron emission tomography 11C-radiolabeling
Miller, Philip W.,Long, Nicholas J.,De Mello, Andrew J.,Vilar, Ramon,Audrain, Helene,Bender, Dirk,Passchier, Jan,Gee, Antony
, p. 2875 - 2878 (2007)
Taking the tube: A silica-supported palladium catalyst packed into teflon tubing is a simple, low-cost, and effective method for carrying out carbonylative cross-coupling reactions of arylhalides with amines and radiolabeled carbon monoxide gas. In carbonylation reactions, the microtube reactor displays enhanced yields over a short time period (12 min) compared with batch methods. (Chemical Equation Presented).
High-load, oligomeric monoamine hydrochloride: facile generation via ROM polymerization and application as an electrophile scavenger
Stoianova, Diana S.,Yao, Lei,Rolfe, Alan,Samarakoon, Thiwanka,Hanson, Paul R.
, p. 4553 - 4555 (2008)
A new high-load, oligomeric monoamine hydrochloride (OMAm·HCl) derived from ring-opening metathesis polymerization (ROMP) of norbornene methylamine is reported. This oligomeric amine has been shown to be an effective scavenger of acid chlorides, sulfonyl chlorides, and isocyanates. The reagent can be synthesized in a straightforward protocol from the Diels-Alder reaction of dicyclopentadiene (DCPD) 1 with allylamine (neat), formation of the corresponding ammonium salt and subsequent ROM polymerization to afford the desired oligomeric ammonium salts.
Ru(II)-Catalyzed C-H Activation: Amide-Directed 1,4-Addition of the Ortho C-H Bond to Maleimides
Keshri, Puspam,Bettadapur, Kiran R.,Lanke, Veeranjaneyulu,Prabhu, Kandikere Ramaiah
, p. 6056 - 6065 (2016)
Maleimide has been used as a selective coupling partner to generate conjugate addition products exclusively. The typical Heck-type oxidative coupling that occurs when alkenes are used is avoided by choosing maleimide as an alkene, which cannot undergo β-hydride elimination due to the unavailability of a syn-periplanar β-hydrogen atom. The amide nitrogen, which is notorious for undergoing tandem reactions to generate spirocyclic or annulation products under cross-coupling conditions, remains innocent in this report. Along with the substrate scope, a robustness screen has been performed to analyze the performance of amide as a directing group in the presence of other directing groups and also to examine the tolerance of the reaction conditions for other frequently encountered functional groups.
In situ synthesis of metallophthalocyanines into pores of MIL-101: A novel and green strategy for preparation of host–guest catalysts
Boroujeni, Mahmoud Borjian,Hashemzadeh, Alireza,Shaabani, Ahmad,Amini, Mostafa M.
, (2017)
A novel strategy is developed to encapsulate metallophthalocyanines (MPcs, M?=?Cu, Ni and Co) into MIL-101 to give MPcs@MIL-101 via in situ synthesis of MPcs from component fragments in 1-butyl-3-methylimidazolium bromide as an ionic liquid. This strategy overcomes some drawbacks of existing methods for encapsulation of MPcs into metal–organic frameworks. The chemical and structural properties of MPcs@MIL-101 were determined using scanning electron microscopy, powder X-ray diffraction, and Fourier transformation infrared and flame atomic absorption spectroscopies. The results showed that CuPc@MIL-101, which was used as a ‘ship-in-a-bottle’ catalyst, demonstrates excellent catalytic performance in the oxidative amidation of aldehydes with amine salts. It is confirmed that CuPc@MIL-101 can be reused up to five times without significant loss of its activity.
Application of thio-Ugi adducts for the preparation of benzo[ b ]thiophene and S-heterocycle library via copper catalyzed intramolecular C-S bond formation
Kim, Yong-Sang,Kwak, Se Hun,Gong, Young-Dae
, p. 365 - 373 (2015)
Fused heterocycles, such as benzo[b]thiophene, thiochroman, benzo[b][1,4]thiazine, and 1,4-benzothiazepine were generated from thio-Ugi adducts containing a thioamide group through copper-catalyzed intramolecular C-S bond formation under microwave irradiation.
Polyethylene glycol as a recyclable reaction medium for gold-catalysed direct oxidative amide synthesis from aldehydes and amines
Jiang, Hui-Liang,Zhao, Jie
, p. 654 - 656 (2015)
Polyethylene glycol (PEG) was used as the recyclable reaction medium for gold-catalysed oxidative amidation of aldehydes with amines by using tert-butyl hydroperoxide (TBHP, 70% aqueous) as the oxidant. The reaction proceeded efficiently to provide the corresponding products in moderate to good yields under mild conditions. Both the catalysts and solvent can be easily recovered and reused by simple extraction without significant loss of activity.
Selective N-Monoalkylation of Amide Derivatives with Trialkyl Phosphates
Asai, Shota,Ban, Kazuho,Monguchi, Yasunari,Sajiki, Hironao,Sawama, Yoshinari
, p. 322 - 325 (2018)
A highly selective and easily handled monoalkylation of primary amide derivatives by using trialkyl phosphates as alkylating reagents in cyclopentyl methyl ether (CPME) was developed. Various monoalkylated amide derivatives were efficiently synthesized by changing the alkyl moiety (e.g., methyl, ethyl, butyl, or benzyl) of the trialkyl phosphate. These phosphate reagents are relatively stable and easily available, and CPME is a useful solvent in process chemistry.
A convenient photocatalytic fluorination of unactivated C-H bonds
Halperin, Shira D.,Fan, Hope,Chang, Stanley,Martin, Rainer E.,Britton, Robert
, p. 4690 - 4693 (2014)
Fluorination reactions are essential to modern medicinal chemistry, thus providing a means to block site-selective metabolic degradation of drugs and access radiotracers for positron emission tomography imaging. Despite current sophistication in fluorination reagents and processes, the fluorination of unactivated C-H bonds remains a significant challenge. Reported herein is a convenient and economic process for direct fluorination of unactivated C-H bonds that exploits the hydrogen abstracting ability of a decatungstate photocatalyst in combination with the mild fluorine atom transfer reagent N-fluorobenzenesulfonimide. This operationally straightforward reaction provides direct access to a wide range of fluorinated organic molecules, including structurally complex natural products, acyl fluorides, and fluorinated amino acid derivatives. The direct fluorination of unactivated C(sp3)-H bonds is catalyzed by the inexpensive photocatalyst tetrabutylammonium decatungstate (TBADT). This convenient reaction provides direct access to a wide range of fluorinated organic molecules, including structurally complex natural products, acyl fluorides, and fluorinated amino acids.
Synthesis of Benzamide Derivatives by the Reaction of Arenes and Isocyanides through a C-H Bond Activation Strategy
Khalaj, Mehdi,Taherkhani, Mahboubeh,Mousavi-Safavi, Seyed Mahmoud,Akbari, Jafar
, p. 94 - 98 (2018)
A carbon-carbon bond formation reaction between isocyanides and benzene derivatives is reported. In contrast to traditional cross-coupling reactions, which require aryl halides or pseudohalides, we use a palladium catalyst to generate the aryl-palladium through C-H bond activation of arenes. This method offers an attractive approach to a range of benzamides from readily accessible benzene derivatives.
A microfluidic approach to the rapid screening of palladium-catalysed aminocarbonylation reactions
Miller, Philip W.,Jennings, Lucy E.,DeMello, Andrew J.,Gee, Antony D.,Long, Nicholas J.,Vilar, Ramon
, p. 3260 - 3268 (2009)
The evaluation and selection of the most appropriate catalyst for a chemical transformation is an important process in many areas of synthetic chemistry. Conventional catalyst screening involving batch reactor systems can be both time-consuming and expensive, resulting in a large number of individual chemical reactions. Continuous flow microfluidic reactors are increasingly viewed as a powerful alternative format for reacting and processing larger numbers of small-scale reactions in a rapid, more controlled and safer fashion. In this study we demonstrate the use of a planar glass microfluidic reactor for performing the three-component palladium-catalysed aminocarbonylation reaction of iodobenzene, benzylamine and carbon monoxide to form N-benzylbenzamide, and screen a series of palladium catalysts over a range of temperatures. N-Benzylbenzamide product yields for this reaction were found to be highly dependent on the nature of the catalyst and reaction temperature. The majority of catalysts gave good to high yields under typical flow conditions at high temperatures (150°C), however the palladium(II) chloride-Xantphos complex [PdCl2 (Xantphos)] proved to be far superior as a catalyst at lower temperatures (75-120°C). The utilised method was found to be an efficent and reliable way for screening a large number of palladium-catalysed carbonylation reactions and may prove useful in screening other gas/liquid phase reactions.
BENZOTRIAZOL-1-YL DIETHYL PHOSPHATE. A NEW CONVENIENT COUPLING REAGENT FOR THE SYNTHESIS OF AMIDES AND PEPTIDES.
Kim, Sunggak,Chang, Heung,Ko, Young Kwan
, p. 1341 - 1342 (1985)
Benzotriazol-1-yl diethyl phosphate is found to be a new convenient coupling reagent for the synthesis of amides and practically racemization-free peptides.
A novel approach for the one-pot preparation of α-amino amides by pd-catalyzed double carbohydroamination
Lin, Yong-Shou,Alper, Howard
, p. 779 - 781 (2001)
A new domino reaction sequence, a palladium-catalyzed double carbohydroamination, which involves double carbonylation, amine condensation, and hydrogenation from an aryl iodide(1), a primary amine (2), and synthetic gas has been realized as a novel synthetic means for the one-pot synthesis of α-amino amides (3).
Direct, rapid, solvent-free conversion of unactivated esters to amides using lithium hydroxide as a catalyst
Miller, Shelli A.,Leadbeater, Nicholas E.
, p. 93248 - 93251 (2015)
A simple, solvent-free methodology is reported for the direct conversion of esters to amides using lithium hydroxide as a catalyst. The approach allows for the preparation of a range of amide products as well as being applicable to the ring-opening of a representative lactone.
Metal-free synthesis of amides by oxidative amidation of aldehydes with amines in PEG/oxidant system
Liang, Jun,Lv, Jing,Shang, Zhi-Cai
, p. 8532 - 8535 (2011)
A simple, inexpensive, and efficient one-pot synthesis of amide derivatives were achieved in good to excellent yields via the directly oxidative amidation of aldehydes with amines under PEG/Oxidant system.
Microwave effects in solvent-free esters aminolysis
Perreux, Laurence,Loupy, André,Delmotte, Michel
, p. 2185 - 2189 (2003)
Solvent-free ester aminolysis was studied under microwave or conventional heating either in the absence of base or induced by KOtBu with or without a phase transfer agent. The specific microwave effects were shown to be dependent on the conditions and discussed in terms of relative polarities of ground and transition states.
Cobalt(III)-Catalyzed Directed C-H Allylation
Gensch, Tobias,Vásquez-Céspedes, Suhelen,Yu, Da-Gang,Glorius, Frank
, p. 3714 - 3717 (2015)
The cobalt(III)-catalyzed allylation was developed for amide-directed C-H activation of arenes, heteroarenes, and olefins. A variety of allyl sources can be employed to introduce this useful functional group.
Notiz zur Aminolyse von Dibenzoyl-peroxid mit primaeren Aminen
Psiorz, Manfred,Zinner, Gerwalt
, p. 217 (1984)
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N-linked hydroxylamine resin: Solid-phase synthesis of hydroxamic acids
Yin, Zheng,Low, KaySiang,Lye, PekLing
, p. 2945 - 2950 (2005)
A novel hydroxylamine resin for solid-phase synthesis of hydroxamic acids is described. Its facile application is illustrated by the solid-phase synthesis of various hydroxamic acids. Cleavage is induced under acidic conditions by treatment with trifluoroacetic acid, providing hydroxamic acids in high purity and good yields. Copyright Taylor & Francis, Inc.
Mukaiyama,T. et al.
, p. 4490 - 4491 (1968)
Computationally motivated synthesis and enzyme kinetic evaluation of N-(β-d-glucopyranosyl)-1,2,4-triazolecarboxamides as glycogen phosphorylase inhibitors
Begum, Jaida,Varga, Gergely,Docsa, Tibor,Gergely, Pl,Hayes, Joseph M.,Juhsz, Lszl,Somsk, Lszl
, p. 80 - 89 (2015)
Following our recent study of N-(β-d-glucopyranosyl)oxadiazolecarboxamides (Polyk et al., Biorg. Med. Chem. 2013, 21, 5738) revealed as moderate inhibitors of glycogen phosphorylase (GP), in silico docking calculations using Glide have been performed on N-(β-d-glucopyranosyl)-1,2,4-triazolecarboxamides with different aryl substituents predicting more favorable binding at GP. The ligands were subsequently synthesized in moderate yields using N-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-tetrazole-5-carboxamide as starting material. Kinetics experiments against rabbit muscle glycogen phosphorylase b (RMGPb) revealed the ligands to be low μM GP inhibitors; the phenyl analogue (Ki = 1 μM) is one of the most potent N-(β-d-glucopyranosyl)-heteroaryl-carboxamide-type inhibitors of the GP catalytic site discovered to date. Based on QM and QM/MM calculations, the potency of the ligands is predicted to arise from favorable intra- and intermolecular hydrogen bonds formed by the most stable solution phase tautomeric (t2) state of the 1,2,4-triazole in a conformationally dynamic system. ADMET property predictions revealed the compounds to have promising pharmacokinetic properties without any toxicity. This study highlights the benefits of a computationally led approach to GP inhibitor design. This journal is
N-heterocyclic carbenes as ligands in palladium-mediated [ 11C]radiolabelling of [11C]amides for positron emission tomography
Jennings, Lucy E.,Kealey, Steven,Miller, Philip W.,Gee, Antony D.,Long, Nicholas J.
, p. 135 - 139 (2011)
A model palladium-mediated carbonylation reaction synthesizing N-benzylbenzamide from iodobenzene and benzylamine was used to investigate the potential of four N-heterocyclic carbenes (N,N′-bis(diisopropylphenyl)-4, 5-dihydroimidazolinium chloride (I), N,N′-bis(1-mesityl)-4,5- dihydroimidazolinium chloride (II), N,N′-bis(1-mesityl)imidazolium chloride (III) and N,N′-bis(1-adamantyl)imidazolium chloride (IV)) to act as supporting ligands in combination with Pd2(dba)3. Their activities were compared with other Pd-diphosphine complexes after reaction times of 10 and 120 min. Pd2(dba)3 and III were the best performing after 10 min reaction (20%) and was used to synthesize radiolabelled [11C]N-benzylbenzamide in good radiochemical yield (55%) and excellent radiochemical purity (99%). A Cu(Tp*) complex was used to trap the typically unreactive and insoluble [11C]CO which was then released and reacted via the Pd-mediated carbonylation process. Potentially useful side products [11C]N,N′-dibenzylurea and [ 11C]benzoic acid were also observed. Increased amounts of [ 11C]N,N′-dibenzylurea were yielded when PdCl2 was the Pd precursor. Reduced yields of [11C]benzoic acid and therefore improved RCP were seen for III/Pd2(dba)3 over commonly used dppp/Pd2(dba)3 making it more favourable in this case. Copyright
Continuous flow reaction system for the synthesis of 2,2,2-trichloroacetophenone derivatives and its application
Ko, Byeng Ha,Yu, Subeen,Song, Kwang Ho,Lee, Sunwoo
, p. 991 - 994 (2018)
A continuous flow reaction system was developed for the synthesis of 2,2,2-trichloroacetophenone derivatives. When aryl propiolic acids and water were mixed with trichloroisocyanuric acid in DMF at 5 °C, the 2,2,2-trichloroacetophenone derivatives were formed within 5 min with good yields. In addition, the resulting mixture was flowed to react with amines to give the corresponding benzamide. This flow reaction system provided higher yields within shorter times than the batch reaction system.
Ligand preferences in ytterbium ions complexation with carboxylate-based metal-organic frameworks
Hashemzadeh, Alireza,Amini, Mostafa M.,Khavasi, Hamid Reza,Ng, Seik Weng
, p. 3217 - 3232 (2017)
Two coordination polymers of ytterbium were synthesized by employing 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoic acid (H3TATB), 4,4′,4-benzene-1,3,5-triyl-tribenzoic acid (H3BTB), and 3,5-pyridinedicarboxylic acid (3,5-PDC) ligands and were characterized by single-crystal X-ray diffraction analysis. Reaction of ytterbium(III) chloride in the presence of H3BTB and 3,5-PDC ligands gives preferred complexation with the 3,5-PDC ligand, producing [Yb2(3,5-PDC)(ClO4)3][NH(Me)3] (1). However, under exactly the same reaction conditions, reaction of ytterbium(III) chloride in the presence of 3,5-PDC and H3TATB resulted in complexation with H3TATB to form [(CH3)2NH2][Yb4(TATB)4(HCO2)(H2O)2]·3H2O (2). The crystal structure results showed a layered structure for 1 and a metal-organic framework structure for 2. This indicates that the complexation preference of the ytterbium ion is H3TATB?≥?3,5-PDC?≥?H3BTB. Conversely, the uncomplexed ligand in the metal-organic framework (2) is an auxiliary agent during the synthesis, which shows polytopic linker controls crystal properties, to form suitable crystals for single-crystal structure determination. The prepared coordination compounds were used as heterogeneous catalysts in an oxidation amidation reaction with different aldehydes and benzylamine hydrochloride.
TBAI-catalyzed C–N bond formation through oxidative coupling of benzyl bromides with amines: a new avenue to the synthesis of amides
Kumar, Dhirendra,Maury, Suresh Kumar,Kumari, Savita,Kamal, Arsala,Singh, Himanshu Kumar,Singh, Sundaram,Srivastava, Vandana
supporting information, p. 424 - 432 (2022/02/09)
A new green approach for the synthesis of amide through TBAI-catalyzed oxidative coupling of benzyl bromides with amine was developed in the presence of tert-butyl hydroperoxide (TBHP) as an oxidant. Various electron-donating and withdrawing groups containing benzyl bromides and various amines, were subjected to the reaction and transformed to the corresponding amide in good to excellent yields.
Photocatalysis in Aqueous Micellar Media Enables Divergent C-H Arylation and N-Dealkylation of Benzamides
Cybularczyk-Cecotka, Martyna,Predygier, J?drzej,Crespi, Stefano,Szczepanik, Joanna,Giedyk, MacIej
, p. 3543 - 3549 (2022/03/27)
Photocatalysis in aqueous micellar media has recently opened wide avenues to activate strong carbon-halide bonds. So far, however, it has mainly explored strongly reducing conditions, restricting the available chemical space to radical or anionic reactivity. Here, we demonstrate a controllable, photocatalytic strategy that channels the reaction of chlorinated benzamides via either a radical or a cationic pathway, enabling a chemodivergent C-H arylation or N-dealkylation. The catalytic system operates under mild conditions with methylene blue as a photocatalyst and blue LEDs as the light source. Factors determining the reactivity of substrates, their selectivity, and preliminary mechanistic studies are presented.
Generation of Oxyphosphonium Ions by Photoredox/Cobaloxime Catalysis for Scalable Amide and Peptide Synthesis in Batch and Continuous-Flow
Chen, Xiangyang,Houk, Kendall N.,Mo, Jia-Nan,Su, Junqi,Umanzor, Alexander,Zhang, Zheng,Zhao, Jiannan
supporting information, (2022/01/06)
Phosphine-mediated deoxygenative nucleophilic substitutions, such as the Mitsunobu reaction, are of great importance in organic synthesis. However, the conventional protocols require stoichiometric oxidants to trigger the formation of the oxyphosphonium i
