- Oxidative amidation of benzaldehyde using a quinone/DMSO system as the oxidizing agent
-
An efficient transition-metal-based heterogeneous catalyst free procedure for obtaining the oxidative amidation of benzaldehyde using quinones as oxidizing agents in low molar proportions is described here. Pyrrolylquinones (PQ) proved to be more suitable
- Mejía-Farfán, Itzel,Solís-Hernández, Manuel,Navarro-Santos, Pedro,Contreras-Celedón, Claudia A.,Cortés-García, Carlos Jesus,Chacón-García, Luis
-
-
Read Online
- Dilithium Amides as a Modular Bis-Anionic Ligand Platform for Iron-Catalyzed Cross-Coupling
-
Dilithium amides have been developed as a bespoke and general ligand for iron-catalyzed Kumada-Tamao-Corriu cross-coupling reactions, their design taking inspiration from previous mechanistic and structural studies. They allow for the cross-coupling of alkyl Grignard reagents with sp2-hybridized electrophiles as well as aryl Grignard reagents with sp3-hybridized electrophiles. This represents a rare example of a single iron-catalyzed system effective across diverse coupling reactions without significant modification of the catalytic protocol, as well as remaining operationally simple.
- Neate, Peter G.N.,Zhang, Bufan,Conforti, Jessica,Brennessel, William W.,Neidig, Michael L.
-
supporting information
p. 5958 - 5963
(2021/08/18)
-
- Cobalt(iii)-catalyzed C-H amidation of: N, N -dialkyl thiobenzamides by sulfur coordination
-
An efficient inexpensive cobalt(iii)-catalyzed intermolecular amidation of N,N-dialkyl thiobenzamides with 1,4,2-dioxazol-5-ones via C-H bond activation is described. The reaction proceeds with high functional group tolerance under external oxidant free conditions, providing a straightforward approach for the direct modification of thioamide derivatives, which are prevalent organic motifs found in vital biological and pharmaceutical molecules. This journal is
- Gao, Pengpeng,Zhang, Xiaohui,Zheng, Qing-Zhong
-
supporting information
p. 10332 - 10336
(2021/12/17)
-
- Method for preparing amide compound by photocatalysis of nitrogen-containing heterocyclic compound
-
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.
- -
-
Paragraph 0089; 0090; 0093; 0094
(2021/06/06)
-
- Visible Light-Driven Efficient Synthesis of Amides from Alcohols using Cu?N?TiO2 Heterogeneous Photocatalyst
-
Amides were synthesized from alcohols and amines in high yields using an in situ generated active ester of N-hydroxyimide with our developed Cu?N?TiO2 catalyst at room temperature using oxygen as a sole oxidant under visible light. The catalyst can be easily prepared, robust, and recycled four times without a considerable change in catalytic activity. This developed protocol applies to a wide substrate scope and has good functional group tolerance. The application of this amidation reaction has been successfully demonstrated for the synthesis of moclobemide, an antidepressant drug, and an analog of the itopride drug on a gram scale.
- Singha, Krishnadipti,Ghosh, Subhash Chandra,Panda, Asit Baran
-
p. 657 - 662
(2021/02/02)
-
- Photocatalytic aldehydes/alcohols/toluenes oxidative amidation over bifunctional Pd/MOFs: Effect of Fe-O clusters and Lewis acid sites
-
Heterogeneous photocatalytic organic synthesis is fascinating because of the utilization of ubiquitous solar light for chemical transformations. Here, three Fe-MOFs with different Fe-O clusters, Lewis acid sites and morphologies were synthesized through coordination structure engineering. Pd/Fe-MOFs nanocomposites were used to challenge the amide bond green synthesis with visible light. Pd/MIL-101(Fe) exhibited the best photocatalytic performance due to the easily excited Fe3-μ3-oxo clusters for light absorption, the efficient photogenerated carriers separation and migration, the large amount of Lewis acid sites based aldehydes and amines condensation promotion and the efficient O2 reduction to superoxide radicals over photogenerated electron-rich Pd NPs. Various aldehydes, alcohols and toluenes could be transformed to amide compounds with amines over Pd/MIL-101(Fe) with just oxygen or air as the green oxidant and water as the by-product. One-pot C–C cross-coupling and photo-redox C–N coupling cascade reactions could also be achieved over Pd/MIL-101(Fe). This work shed light on the efficient and sustainable amide bonds synthesis.
- Bian, Fengxia,Cheng, Hongmei,Jiang, Heyan,Sun, Bin,Tan, Jiangwei,Zang, Cuicui
-
p. 279 - 287
(2021/08/21)
-
- Visible-Light-Mediated Oxidative Amidation of Aldehydes by Using Magnetic CdS Quantum Dots as a Photocatalyst
-
A magnetic CdS quantum dot (Fe3O4/polydopamine (PDA)/CdS) was synthesized through a facile and convenient method from inexpensive starting materials. Characterization of the prepared catalyst was performed by means of FTIR spectrosco
- Xu, Ling,Zhang, Shuai-Zheng,Li, Wei,Zhang, Zhan-Hui
-
p. 5483 - 5491
(2021/03/01)
-
- Amide Bond Formation via Aerobic Photooxidative Coupling of Aldehydes with Amines Catalyzed by a Riboflavin Derivative
-
We report an effective, operationally simple, and environmentally friendly system for the synthesis of tertiary amides by the oxidative coupling of aromatic or aliphatic aldehydes with amines mediated by riboflavin tetraacetate (RFTA), an inexpensive organic photocatalyst, and visible light using oxygen as the sole oxidant. The method is based on the oxidative power of an excited flavin catalyst and the relatively low oxidation potential of the hemiaminal formed by amine to aldehyde addition.
- Hassan Tolba, Amal,Krupi?ka, Martin,Chudoba, Josef,Cibulka, Radek
-
supporting information
p. 6825 - 6830
(2021/09/11)
-
- Visible-Light-Driven C-N Bond Formation by a Hexanickel Cluster Substituted Polyoxometalate-Based Photocatalyst
-
A powerful and attractive route to develop novel photocatalysts for C-N bond formation involves the use of pyrrolidine as the substrate and cocatalyst simultaneously. Herein, a new polyoxometalate (POM)-based metal-organic framework, namely, [Ni6(OH)3(H2O
- Chang, Jiangnan,Han, Qiuxia,Jiao, Jiachen,Li, Jie,Li, Mingxue
-
p. 10022 - 10029
(2021/07/19)
-
- Ruthenium(II)-catalyzed C-H arylation of N,N-dialkyl thiobenzamides with boronic acids by sulfur coordination in 2-MeTHF
-
We report ruthenium(II)-catalyzed ortho-C-H arylation of N,N-dialkylthiobenzamides with boronic acids. The method employs [RuCl2(p-cym)]2 in the presence of Cu(OTf)2 and Ag2O oxidant. The reaction represents the first example of Ru-catalyzed C-H arylation directed by sulfur-containing groups and a rare example of C-H arylation directed by the versatile thiobenzamide moiety. As a further advantage, the method is performed in sustainable and eco-friendly 2-MeTHF as a solvent.
- Zhang, Jin,Liu, Ying,Jia, Qiangqiang,Wang, Yue,Ma, Yangmin,Szostak, Michal
-
supporting information
p. 6884 - 6890
(2020/09/15)
-
- Amidation of Aldehydes with Amines under Mild Conditions Using Metal-Organic Framework Derived NiO@Ni Mott-Schottky Catalyst
-
Here we report a facile method for the synthesis of nickel oxide-nickel (NiO@Ni) Mott-Schottky catalyst employing metal-organic framework (MOF) as the precursor. A direct amidation protocol of aldehydes with amines has been optimized under mild conditions using NiO@Ni Mott-Schottky catalyst and it shows far better catalytic activity than the NiO?Ni nanoparticles prepared from simple Ni2+ salt under similar reaction conditions. The heterogeneous catalyst is robust, recyclable and efficient to provide comparable yield to costly ligand-based homogeneous Ni catalysts. The scope of the reaction protocol has been explored with variably substituted substrates. The reaction initiates by homolytic cleavage of peroxide and proceeds through radical mechanism.
- Goel, Bharat,Vyas, Ved,Tripathi, Nancy,Kumar Singh, Ajit,Menezes, Prashanth W.,Indra, Arindam,Jain, Shreyans K.
-
p. 5743 - 5749
(2020/09/09)
-
- Method for synthesizing amide compounds by using N-Boc amide as substrate
-
The invention relates to a method for synthesizing amide compounds by using N-Boc amide as a substrate. According to the method, N-Boc amide and various amine compounds are subjected to an intermolecular nucleophilic substitution reaction in an organic solvent so as to efficiently prepare various amide compounds. The method has the advantages of mild reaction conditions, simple and convenient operation, high yield and good functional group compatibility.
- -
-
Paragraph 0039-0047
(2020/01/12)
-
- N-Doped Yellow TiO2 Hollow Sphere-Mediated Visible-Light-Driven Efficient Esterification of Alcohol and N-Hydroxyimides to Active Esters
-
Herein we report a simple synthetic protocol for N-doped yellow TiO2 (N-TiO2) hollow spheres as an efficient visible-light-active photocatalyst using aqueous titanium peroxocarbonate complex (TPCC) solution as precursor and NH4OH. In the developed strategy, the ammonium ion of TPCC and NH4OH acts as nitrogen source and structure-directing agent. The synthesized N-TiO2 hollow spheres are capable of promoting the synthesis of active esters of N-hydroxyimide and alcohol through simultaneous selective oxidation of alcohol to aldehyde followed by cross-dehydrogenative coupling (CDC) under ambient conditions upon irradiation of visible light. It is possible to develop a novel and cost-effective one-pot strategy for the synthesis of important esters and amides on gram scale using the developed strategy. The catalytic activity of N-TiO2 hollow spheres is much superior to that of other reported N-TiO2 samples as well as TiO2 with varying morphology.
- Singha, Krishnadipti,Ghosh, Subhash Ch.,Panda, Asit Baran
-
p. 3205 - 3212
(2019/09/09)
-
- Unexpected resistance to base-catalyzed hydrolysis of nitrogen pyramidal amides based on the 7-azabicyclic[2.2.1]heptane scaffold
-
Non-planar amides are usually transitional structures, that are involved in amide bond rotation and inversion of the nitrogen atom, but some ground-minimum non-planar amides have been reported. Non-planar amides are generally sensitive to water or other n
- De Velasco, Diego Antonio Ocampo Gutiérrez,Su, Aoze,Zhai, Luhan,Kinoshita, Satowa,Otani, Yuko,Ohwada, Tomohiko
-
-
- Facile direct synthesis of amides from trichloroethyl esters using catalytic DBU
-
A practical method for the direct synthesis of amide compounds is described. Using small quantities of DBU as a catalyst, the direct conversion of 2,2,2-trichloroethyl esters to their corresponding amides was readily achieved. Based on this protocol, various amide compounds were successfully synthesized in high yield, suggesting a promising approach for the practical one-pot aminolysis from 2,2,2-trichloroethyl protected esters.
- La, Minh Thanh,Kim, Hee-Kwon
-
p. 1135 - 1141
(2018/11/25)
-
- Transamidation of: N -acyl-glutarimides with amines
-
The development of new transamidation reactions for the synthesis of amides is an important and active area of research due to the central role of amide linkage in various fields of chemistry. Herein, we report a new method for transamidation of N-acyl-glutarimides with amines under mild, metal-free conditions that relies on amide bond twist to weaken amidic resonance. A wide range of amines and functional groups, including electrophilic substituents that would be problematic in metal-catalyzed protocols, are tolerated under the reaction conditions. Mechanistic experiments implicate the amide bond twist, thermodynamic stability of the tetrahedral intermediate and leaving group ability of glutarimide as factors controlling the reactivity of this process. The method further establishes the synthetic utility of N-acyl-glutarimides as bench-stable, twist-perpendicular, amide-based reagents in acyl-transfer reactions by a metal-free pathway. The origin of reactivity of N-acyl-glutarimides in metal-free and metal-catalyzed processes is discussed and compared.
- Liu, Yongmei,Achtenhagen, Marcel,Liu, Ruzhang,Szostak, Michal
-
p. 1322 - 1329
(2018/03/06)
-
- One-Pot Tandem Photoredox and Cross-Coupling Catalysis with a Single Palladium Carbodicarbene Complex
-
The combination of conventional transition-metal-catalyzed coupling (2 e? process) and photoredox catalysis (1 e? process) has emerged as a powerful approach to catalyze difficult cross-coupling reactions under mild reaction conditions. Reported is a palladium carbodicarbene (CDC) complex that mediates both a Suzuki–Miyaura coupling and photoredox catalysis for C?N bond formation upon visible-light irradiation. These two catalytic pathways can be combined to promote both conventional transition-metal-catalyzed coupling and photoredox catalysis to mediate C?H arylation under ambient conditions with a single catalyst in an efficient one-pot process.
- Hsu, Yu-Cheng,Wang, Vincent C.-C.,Au-Yeung, Ka-Chun,Tsai, Chung-Yu,Chang, Chun-Chi,Lin, Bo-Chao,Chan, Yi-Tsu,Hsu, Chao-Ping,Yap, Glenn P. A.,Jurca, Titel,Ong, Tiow-Gan
-
supporting information
p. 4622 - 4626
(2018/03/21)
-
- Exploring organic photosensitizers based on hemicyanine derivatives: a sustainable approach for preparation of amide linkages
-
Hemicyanine derivatives C1-C4 have been synthesized and show strong absorption in the visible region, good water solubility, efficient intersystem crossing, a high singlet oxygen quantum yield and high ability to transport electrons from the donor to acceptor. These hemicyanine derivatives were utilized as photocatalysts in additive/base free oxidative amidation of aromatic aldehydes in mixed aqueous media under visible light irradiation at low catalytic loading. The hemicyanine derivative C4 exhibited recyclability upto four cycles and reusability upto five cycles in oxidative amidation of aromatic aldehydes. Among all the hemicyanine derivatives, C4 shows a high photocatalytic efficiency due to a high singlet oxygen quantum yield. All the mechanism investigations showed involvement of reactive oxygen species generated by the organic triplet photosensitizer based on hemicyanine derivative for carrying out oxidative amidation of aldehyde. Our results will encourage the design of new “metal free” organic photosensitizers and their application in photocatalysis.
- Deol, Harnimarta,Kumar, Manoj,Bhalla, Vandana
-
p. 31237 - 31245
(2018/09/13)
-
- Electrogenerated superoxide anion induced oxidative amidation of benzoin
-
Amide function is very important in both organic and medicinal chemistry. Benzamides can be obtained in good to high yields by reaction of benzoin, primary or secondary amines, molecular oxygen and electrogenerated superoxide anion (obtained with galvanos
- Pandolfi, Fabiana,Chiarotto, Isabella,Rocco, Daniele,Feroci, Marta
-
p. 358 - 367
(2017/10/06)
-
- Direct, efficient NHC-catalysed aldehyde oxidative amidation:: In situ formed benzils as unconventional acylating agents
-
A new N-heterocyclic carbene-catalysed oxidative amidation of aldehydes has been developed which converts the aldehyde to a benzil acylating agent in situ. The process uses an air-recyclable oxidant and a nucleophilic co-catalyst and does not require the use of a large excess of either one coupling partner or catalyst.
- Kumar, Vikas,Connon, Stephen J.
-
supporting information
p. 10212 - 10215
(2017/09/22)
-
- Copper-Catalyzed Aerobic Oxidative Amidation of Benzyl Alcohols
-
A Cu-catalyzed synthesis of amides from alcohols and secondary amines using the oxygen in air as the terminal oxidant has been developed. The methodology is operationally simple requiring no high pressure equipment or handling of pure oxygen. The commercially available, nonprecious metal catalyst, Cu(phen)Cl2, in conjunction with di-tert-butyl hydrazine dicarboxylate and an inorganic base provides a variety of benzamides in moderate to excellent yields. The pKa of amine conjugate acid and electronics of alcohol were shown to impact the selection of base for optimal reactivity. A mechanism consistent with the observed reactivity trends, KIE, and Hammett study is proposed.
- Krabbe, Scott W.,Chan, Vincent S.,Franczyk, Thaddeus S.,Shekhar, Shashank,Napolitano, José G.,Presto, Carmina A.,Simanis, Justin A.
-
p. 10688 - 10697
(2016/11/29)
-
- Aminofluorene-Mediated Biomimetic Domino Amination-Oxygenation of Aldehydes to Amides
-
A conceptually novel biomimetic strategy based on a domino amination-oxygenation reaction was developed for direct amidation of aldehydes under metal-free conditions employing molecular oxygen as the oxidant. 9-Aminofluorene derivatives acted as pyridoxamine-5′-phosphate equivalents for efficient, chemoselective, and operationally simple amine-transfer oxygenation reaction. Unprecedented RNH transfer involving secondary amine to produce secondary amides was achieved. In the presence of 18O2, 18O-amide was formed with excellent (95%) isotopic purity.
- Ghosh, Santanu,Jana, Chandan K.
-
supporting information
p. 5788 - 5791
(2016/11/29)
-
- Synthesis of Ag/g-C3N4Composite as Highly Efficient Visible-Light Photocatalyst for Oxidative Amidation of Aromatic Aldehydes
-
In this contribution, an Ag/g-C3N4nanocomposite was synthesized and utilized as highly efficient and green photocatalyst for organic reactions under visible light irradiation. A layered, porous g-C3N4was synthes
- Wang, Lingling,Yu, Min,Wu, Chaolong,Deng, Nan,Wang, Chao,Yao, Xiaoquan
-
p. 2631 - 2641
(2016/08/31)
-
- Palladium nanoparticles immobilized on an amine-functionalized MIL-101(Cr) as a highly active catalyst for oxidative amination of aldehydes
-
The present work reports the synthesis of well dispersed palladium nanoparticles immobilized on an amino functionalized nanoscale metal-organic framework MIL-101(Cr), by using a facile polyol method. The resulting Pd/NH2-MIL-101(Cr) nanocomposite is established to be an active heterogeneous catalyst for oxidative amination of aldehydes under solvent free conditions using hydrogen peroxide as an oxidant. The synthesized Pd/NH2-MIL-101(Cr) is characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, field emission scanning electron microscopy, Brunauer-Emmett-Teller (BET) surface area analysis, Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and atomic absorption spectroscopy (AAS). The catalyst could easily be recovered and recycled without any significant loss of its catalytic activity.
- Saikia, Mrinal,Saikia, Lakshi
-
p. 14937 - 14947
(2016/02/19)
-
- BODIPY catalyzed amide synthesis promoted by BHT and air under visible light
-
A novel and efficient protocol for the synthesis of amides is reported which employs a BODIPY catalyzed oxidative amidation reaction between aromatic aldehydes and amines under visible light. Compared with the known Ru or Ir molecular catalysts and other organic dyes, the BODIPY catalyst showed higher reactivity toward this reaction. Mechanistic studies reveal that dioxygen could be activated through an ET and a SET pathway, forming active peroxides in situ, which are vital for the key step of the reaction, i.e. the oxidation of hemiaminal to amide. The broad substrate scope and mild reaction conditions make this reaction practically useful and environmentally friendly for the synthesis of amide compounds.
- Wang, Xiao-Fei,Yu, Shu-Sheng,Wang, Chao,Xue, Dong,Xiao, Jianliang
-
p. 7028 - 7037
(2016/07/30)
-
- Catalytic Formation of α-Aryl Ketones by C-H Functionalization with Cyclic Alkenyl Carbonates and One-Pot Synthesis of Isocoumarins
-
We report here a method for direct catalytic introduction of simple α-acylalkyl groups via rhodium-catalyzed C-H functionalization with cyclic alkenyl carbonates, synthetic equivalents to enolates bearing leaving groups. The reaction proceeded smoothly without using bases to give α-aryl ketones in high yields. Various nitrogen-containing aromatic rings and amide groups serve as directing groups. 3-Substituted isocoumarins can also be prepared by one-pot C-H functionalization/cyclization.
- Hara, Yusuke,Onodera, Shunsuke,Kochi, Takuya,Kakiuchi, Fumitoshi
-
supporting information
p. 4850 - 4853
(2015/10/12)
-
- Mild and selective Et2Zn-catalyzed reduction of tertiary amides under Hydrosilylation conditions
-
Diethylzinc (Et2Zn) can be used as an efficient and chemoselective catalyst for the reduction of tertiary amides under mild reaction conditions employing cost-effective polymeric silane (PMHS) as the hydride source. Crucial for the catalytic activity was the addition of a substoichiometric amount of lithium chloride to the reaction mixture. A series of amides containing different additional functional groups were reduced to their corresponding amines, and the products were isolated in good-to-excellent yields.
- Kovalenko, Oleksandr O.,Volkov, Alexey,Adolfsson, Hans
-
supporting information
p. 446 - 449
(2015/03/05)
-
- Investigating Scale-Up and Further Applications of DABAL-Me3 Promoted Amide Synthesis
-
Methods for the batch scale up of DABAL-Me3 promoted direct ester to amide synthesis have been demonstrated at 10-100 g scales using a tert-amide model compound. Procedures for 20 g scale couplings in standard laboratory glassware and up to 0.1 kg in industry-standard jacketed glass reactors in near quantitative yields are given. A derivative of the anticancer agent Imatinib (Gleevec) has been synthesized on a 26 g scale (98% yield, >98% purity) establishing DABAL-Me3 as a potential alternative for the synthesis of amides in API scale preparations. Continuous flow methodology provides a method for larger scales (productivities of >50 g h-1). In addition, nitriles were coupled to primary amines and hydrazines with DABAL-Me3, resulting in the clean formation of free amidines (16 examples) and amidrazones.
- Lee, Darren S.,Amara, Zacharias,Poliakoff, Martyn,Harman, Thomas,Reid, Gary,Rhodes, Barrie,Brough, Steve,McInally, Thomas,Woodward, Simon
-
supporting information
p. 831 - 840
(2015/07/27)
-
- Anionic phenoxy-amido rare-earth complexes as efficient catalysts for amidation of aldehydes with amines
-
A series of anionic organo-rare-earth amido complexes stabilized by dianionic phenoxy-amido ligands were prepared and their catalytic behavior for amidation reactions of aldehydes with amines was elucidated. Amine elimination reaction of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with an equimolar of lithium aminophenoxy {[HNO]1Li(THF)}2, which was prepared by the reaction of [HNOH]1 {[HNOH]1 = N-p-fluoro-phenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine} with one equivalent of n-BuLi in tetrahydrofuran (THF) in situ, gave the anionic phenoxy-amido rare earth amido complexes [NO]12Ln[N(SiMe3)2][Li(THF)]2 [Ln = Y (1), Yb (2), Sm (3), Nd (4)] in high isolated yields. Similar reactions of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with {[HNO]2Li(THF)}2, and {[HNO]3Li(THF)}2 in THF gave the anionic rare-earth amides [NO]22Ln[N(SiMe3)2][Li(THF)]2 [Ln = Sm (5), Nd (6)] and [NO]32Ln[N(SiMe3)2][Li(THF)]2 [Ln = Sm (7), Nd (8)] {[HNOH]2 = N-p-chloro-phenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine; [HNOH]3 = N-p-bromo-phenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine}, respectively. All of these complexes were fully characterized. X-ray structural determination revealed that these complexes are isostructural, and have solvated monomeric structures. Each of the rare-earth ions is coordinated by two phenoxy-amido ligands and one N(SiMe3)2 group, and the coordination geometry can be described as a distorted trigonal bipyramid. Each of the lithium atoms is surrounded by one aryloxo group, one amido group and one THF molecule, and the coordination geometry can be described as a trigonal plane. The catalytic behavior of these rare-earth amides for the amidation reaction of aldehyde with amine was elucidated. It was found that these complexes are efficient catalysts for this transformation to produce amides in good to excellent yields under mild reaction conditions, and in some cases, diacylamide compounds can be prepared conveniently.
- Wang, Chao,Huang, Lingling,Lu, Min,Zhao, Bei,Wang, Yaorong,Zhang, Yong,Shen, Qi,Yao, Yingming
-
p. 94768 - 94775
(2015/11/24)
-
- Direct allylation of aromatic and α,β-unsaturated carboxamides under ruthenium catalysis
-
The ruthenium-catalyzed oxidative allylation of aromatic and α,β-unsaturated carboxamides with allylic carbonates is described. These transformations proceed readily with complete linear γ-selectivity of substituted allylic carbonates. the Partner Organisations 2014.
- Kim, Mirim,Sharma, Satyasheel,Mishra, Neeraj Kumar,Han, Sangil,Park, Jihye,Kim, Minyoung,Shin, Youngmi,Kwak, Jong Hwan,Han, Sang Hoon,Kim, In Su
-
p. 11303 - 11306
(2014/11/07)
-
- Asymmetric synthesis of α-branched amines via Rh(III)-catalyzed C-H bond functionalization
-
The first asymmetric intermolecular addition of non-acidic C-H bonds to imines is reported. The use of the activating N-perfluorobutanesulfinyl imine substituent is essential for achieving sufficient reactivity and provides outstanding diastereoselectivit
- Wangweerawong, Apiwat,Bergman, Robert G.,Ellman, Jonathan A.
-
supporting information
p. 8520 - 8523
(2014/07/07)
-
- Phenazinium salt-catalyzed aerobic oxidative amidation of aromatic aldehydes
-
Amides are prevalent in organic synthesis. Developing an efficient synthesis that avoids expensive oxidants and heating is highly desirable. Here the oxidative amidation of aromatic aldehydes is reported using an inexpensive metal-free visible light photocatalyst, phenazine ethosulfate, at low catalytic loading (1-2 mol %). The reaction proceeds at ambient temperature and uses air as the sole oxidant. The operationally easy procedure provides an economical, green, and mild alternative for the formation of amide bonds.
- Leow, Dasheng
-
supporting information
p. 5812 - 5815
(2015/02/19)
-
- Silica nanosphere-supported palladium(II) furfural complex as a highly efficient and recyclable catalyst for oxidative amination of aldehydes
-
The present work reports the fabrication of a novel and highly efficient silica nanospheres-based palladium catalyst (SiO2@APTES@Pd-FFR) via immobilization of a palladium complex onto silica nanospheres functionalized with 3-aminopropyltriethoxysilane (APTES), and its catalytic application for the oxidative amination of aldehydes to yield commercially important amides. The structure of the nano-catalyst was confirmed by Solid-state 13C CPMAS and 29Si CPMAS NMR spectroscopy, Brunauer-Emmett-Teller (BET) surface area analysis, Fourier transform infrared spectroscopy (FT-IR), Energy dispersive X-ray fluorescence spectroscopy (ED-XRF), Atomic absorption spectroscopy (AAS), Transmission electron microscopy (TEM) and elemental analysis. The nano-catalyst was found to be highly effective for the oxidative amination of aldehydes using hydrogen peroxide as an environmentally benign oxidant to give amides. The effect of various reaction parameters such as temperature, amount of catalyst, reaction time, type of solvent, oxidant used, substrate to oxidant ratio etc. have been demonstrated to achieve high catalytic efficacy. Moreover, this nanostructured catalyst could be recovered with simplicity and reused for several cycles without any significant loss in its catalytic activity. In addition, the stability of the reused nano-catalyst was proved by FT-IR and HRTEM techniques. It is worth noting that the features of mild reaction conditions, simple work-up procedure, high product yield, no use of toxic organic solvents, high turn-over frequency (TOF), and easy recovery and reusability of the present quasi-homogeneous nano-catalyst make this protocol an attractive alternative to the existing catalytic methods for the oxidative amination of aldehydes to furnish industrially important amides. The Royal Society of Chemistry 2014.
- Sharma,Sharma, Shivani
-
p. 1292 - 1304
(2014/01/06)
-
- Iron/tetramethylethylenediamine-catalyzed ambient-temperature coupling of alkyl grignard reagents and aryl chlorides
-
Tetramethylethylenediamine (TMEDA) acts as cheap and readily removed ligand in the iron-catalyzed coupling of alkyl Grignard reagents and activated aryl chlorides. The use of TMEDA allows for low ligand and iron catalyst loading as well as an increased reaction concentration and an ambient reaction temperature on a mole scale.
- Rushworth, Philip J.,Hulcoop, David G.,Fox, David J.
-
p. 9517 - 9521
(2013/10/08)
-
- Organocatalytic amidation and esterification of aldehydes with activating reagents by a cross-coupling strategy
-
Formation on demand: An organocatalytic cross-coupling reaction of aldehydes with N-hydroxyimides, hexafluoroisopropyl alcohol, and sulfonimides has been developed. The resulting active intermediates can be directly converted into amides or esters in one pot. This simple method makes use of readily available starting materials, and the newly discovered activating reagents should find broad application in the synthesis of amides and esters. Copyright
- Tan, Bin,Toda, Narihiro,Barbas III, Carlos F.
-
supporting information
p. 12538 - 12541
(2013/02/22)
-
- Gold-catalyzed amide synthesis from aldehydes and amines in aqueous medium
-
An efficient gold-catalyzed amide synthesis from aldehydes and amines in aqueous medium under mild reaction conditions has been developed.
- Li, Gai-Li,Kung, Karen Ka-Yan,Wong, Man-Kin
-
supporting information; experimental part
p. 4112 - 4114
(2012/06/16)
-
- Direct oxidative amidation of aromatic aldehydes using aqueous hydrogen peroxide in continuous flow microreactor systems
-
A practical and economical protocol has been developed for the direct oxidative amidation of aromatic aldehydes with secondary amines to synthesize amides in a single operation under mild conditions within 15-40 min. The utilization of aqueous hydrogen peroxide affords a clean synthetic route. No catalysts or promoting reagents are required.
- Liu, Xiaoying,Jensen, Klavs F.
-
supporting information; experimental part
p. 1471 - 1474
(2012/06/04)
-
- Hydrogen peroxide mediated efficient amidation and esterification of aldehydes: Scope and selectivity
-
An efficient method for the amidation and esterification of aldehydes utilizing hydrogen peroxide as an oxidant has been developed. Cyclic amines and primary alcohols selectively reacted with aromatic aldehydes under mild conditions to yield the corresponding amides and esters.
- Tank, Rekha,Pathak, Uma,Vimal, Manorama,Bhattacharyya, Shubhankar,Pandey, Lokesh Kumar
-
p. 3350 - 3354
(2012/01/06)
-
- Synthesis and structural diversity of heterobimetallic lanthanide-potassium complexes and catalytic activity for amidation of aldehydes with amines
-
Four heterobimetallic lanthanide-potassium complexes stabilized by the carbon-bridged bis(phenolate) ligand MBMP2- (MBMP = 2,2′-methylene bis(6-tert-butyl-4-methylphenolate)), [{(MBMP) 2La(THF)2}2K][K(THF)6] (1), [(MBMP)Nd(μ-MBMP)K(THF)]2 (2), [(THF)2Sm(MBMP) 2K(THF)2] (3), and [(THF)2Yb(MBMP) 2K(THF)3] (4), were synthesized, and their structural features were provided. It was found that the ionic radii of lanthanide metals have a profound effect on the structures of the heterobimetallic complexes. Complexes 1 to 4 are efficient catalysts for amidation reactions of aldehydes with amines to produce amides in good to excellent yields under mild conditions.
- Xu, Bin,Huang, Lingling,Yang, Zijian,Yao, Yingming,Zhang, Yong,Shen, Qi
-
experimental part
p. 3588 - 3595
(2011/09/12)
-
- Heterobimetallic complexes of lanthanide and lithium metals with dianionic guanidinate ligands: Syntheses, structures and catalytic activity for amidation of aldehydes with amines
-
Reactions of triguanidinate lanthanide complexes Ln[(iPrN)(NC6H4p-Cl)C(NHiPr)]3 (Ln = Nd, Y) with 3 equiv. of n-BuLi gave [Li(THF)(DME)]3Ln[μ-η2η1 (iPrN)2C(NC6H4p-Cl)]3, which represents the first structurally characterized complexes of lanthanide and lithium metals with dianionic guanidinate ligands. The Nd complex was found to be an effective catalyst for amidation of aldehydes with amines under mild conditions with a wide scope of substrates.
- Qian, Cunwei,Zhang, Xingmin,Zhang, Yong,Shen, Qi
-
experimental part
p. 747 - 752
(2010/04/27)
-
- Heterobimetallic lanthanide/sodium phenoxides: Efficient catalysts for amidation of aldehydes with amines
-
Heterobimetallic lanthanide/sodium phenoxides were found to be efficient catalysts for amidation of aldehydes with amines under mild conditions. The reactivity follows the order Nd 2C6H3O iPr) 2C6H3O 2C 6H3O for phenoxide groups. In comparison with the corresponding monometallic complexes, heterobimetallic complexes show higher activity and a wider range of scope of amines. A cooperation of lanthanide and sodium in this process is proposed to contribute to the high activity of the present catalyst.
- Li, Junmei,Xu, Fan,Zhang, Yong,Shen, Qi
-
supporting information; experimental part
p. 2575 - 2577
(2009/07/18)
-
- Anionic bridged bis(amidinate) lithium lanthanide complexes: Efficient bimetallic catalysts for mild amidation of aldehydes with amines
-
Anionic bridged bis(amidinate) lithium lanthanide complexes have been found to be efficient catalysts for the amidation of aldehydes with amines under mild conditions. The activity follows the order : yttrium neodymium europium ytterbium. The catalysts are available for the formation of benzamides derived from pyrrolidine, piperidine, and morpholine with good to excellent yields. In comparison with the corresponding neutral complexes, the anionic complexes show higher activity and a wider range of scope for the amines. A cooperation of the lanthanide and lithium metals in this process is proposed to contribute to the high activity of the present catalyst.
- Wang, Junfeng,Li, Junmei,Xu, Fan,Shen, Qi
-
supporting information; experimental part
p. 1363 - 1370
(2009/12/09)
-
- Metal-free one-pot oxidative amination of aldehydes to amides
-
Metal-free oxidative amination of aromatic aldehydes in the presence of TBHP provides convenient access to amides in 85-99% under mild reaction conditions within 5 h. This method avoids free carboxylic acid intermediates and integrates aldehyde oxidation and amide bond formation, which are usually accomplished separately, into a single operation. Proline-derived amides can be prepared in excellent yields without noticeable racemization.
- Ekoue-Kovi, Kekeli,Wolf, Christian
-
p. 3429 - 3432
(2008/02/12)
-
- Synthesis of 11C-amides using [11C]carbon monoxide and in situ activated amines by palladium-mediated carboxaminations
-
[11C]Carbon monoxide at low concentrations, aryl halides and amines were used in the palladium-mediated synthesis of twenty 11C-amides. In the study several approaches to improve the radiochemical yield were explored. Eight of the selected amides were prepared by in situ activation of the amines using lithium bis(trimethylsilyl)amide and the radiochemical yields of these reactions were improved compared to utilising a previous reported method. In the synthesis of 1-[carbonyl-11C]benzoyl-3-methyl-1H-indole (11) from 3-methyl-1H-indole (25), the corresponding organotin-amine was prepared prior to the acylation reaction. In a typical experiment, N-(4-hydroxyphenyl)-[carbonyl-11C]acetamide (5) was prepared in 15% radiochemical yield using 4-aminophenol (20) but the yield increased to 63% when the amine was activated by lithium bis(trimethylsilyl)amide.
- Karimi, Farhad,Langstroem, Bengt
-
p. 541 - 546
(2007/10/03)
-
- An Evaluation of Amide Group Planarity in 7-Azabicyclo[2.2.1]heptane Amides. Low Amide Bond Rotation Barrier in Solution
-
Here we show that amides of bicyclic 7-azabicyclo[2.2.1]heptane are intrinsically nitrogen-pyramidal. Single-crystal X-ray diffraction structures of some relevant bicyclic amides, including the prototype N-benzoyl-7-azabicyclo[2.2.1]heptane, exhibited nitrogen-pyramidalization in the solid state. We evaluated the rotational barriers about the amide bonds of various N-benzoyl-7-azabicyclo[2.2.1]heptanes in solution. The observed reduction of the rotational barriers of the bicyclic amides, as compared with those of the monocyclic pyrrolidine amides, is consistent with a nitrogen-pyramidal structure of 7-azabicyclo[2.2.1]heptane amides in solution. A good correlation was found between the magnitudes of the rotational barrier of N-benzoyl-7-azabicyclo[2.2.1]heptanes bearing para-substituents on the benzoyl group and the Hammett's σp+ constants, and this is consistent with the similarity of the solution structures. Calculations with the density functional theory reproduced the nitrogen-pyramidal structures of these bicyclic amides as energy minima. The calculated magnitudes of electron delocalization from the nitrogen nonbonding nN orbital to the carbonyl π* orbital of the amide group evaluated by application of the bond model theory correlated well with the rotational barriers of a variety of amides, including amides of 7-azabicyclo[2.2.1]heptane. The nonplanarity of the amide nitrogen of 7-azabicyclo[2.2.1]heptanes would be derived from nitrogen-pyramidalization due to the CNC angle strain and twisting of the amide bond due to the allylic strain.
- Otani, Yuko,Nagae, Osamu,Naruse, Yuji,Inagaki, Satoshi,Ohno, Masashi,Yamaguchi, Kentaro,Yamamoto, Gaku,Uchiyama, Masanobu,Ohwada, Tomohiko
-
p. 15191 - 15199
(2007/10/03)
-