- Amide Bond Formation via the Rearrangement of Nitrile Imines Derived from N-2-Nitrophenyl Hydrazonyl Bromides
-
We report how the rearrangement of highly reactive nitrile imines derived from N-2-nitrophenyl hydrazonyl bromides can be harnessed for the facile construction of amide bonds. This amidation reaction was found to be widely applicable to the synthesis of primary, secondary, and tertiary amides and was used as the key step in the synthesis of the lipid-lowering agent bezafibrate. The orthogonality and functional group tolerance of this approach was exemplified by the N-acylation of unprotected amino acids.
- Boyle, Mhairi,Livingstone, Keith,Henry, Martyn C.,Elwood, Jessica M. L.,Lopez-Fernandez, J. Daniel,Jamieson, Craig
-
supporting information
p. 334 - 338
(2022/01/20)
-
- Generation of Oxyphosphonium Ions by Photoredox/Cobaloxime Catalysis for Scalable Amide and Peptide Synthesis in Batch and Continuous-Flow
-
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
- Chen, Xiangyang,Houk, Kendall N.,Mo, Jia-Nan,Su, Junqi,Umanzor, Alexander,Zhang, Zheng,Zhao, Jiannan
-
supporting information
(2022/01/06)
-
- Solar and visible-light active nano Ni/g-C3N4photocatalyst for carbon monoxide (CO) and ligand-free carbonylation reactions
-
In this study, we investigate the amino and alkoxycarbonylation reaction between various substituted aryl halides, benzyl iodides, and iodocyclohexane with different types of amines and alcohols in the absence of carbon monoxide gas and ligands. Similar reactions are carried out at high temperatures, in the presence of appropriate ligands, stoichiometric amounts of bases, and gaseous carbon monoxide, which endanger the health of organic chemists. We present a novel method that does not utilize ligands, bases, gaseous CO, and special conditions. This procedure is a redox reaction carried out by new economic nano Ni/g-C3N4at room temperature and under visible light. Mo(CO)6was used toin situgenerate CO, to resolve the problems caused by the use of CO gas. This protocol has the ability to be used on a gram scale by using a continuous flow reactor.
- Hosseini-Sarvari, Mona,Akrami, Zahra
-
p. 956 - 969
(2021/02/26)
-
- NaI-mediated oxidative amidation of benzyl alcohols/aromatic aldehydes to benzamides via electrochemical reaction
-
In this research, we have developed a mild electrochemical process for oxidative amidation of benzyl alcohols/aromatic aldehydes with cyclic amines into the corresponding benzamides. This electroorganic synthetic method proceeds using NaI as a redox mediator under ambient temperature in undivided cell, providing more than 25 examples of amide products in moderate to good yields. The benefits of this reaction include one-pot synthesis, open air condition, proceed in aqueous media and no requirement of external conducting salt, base and oxidant.
- Rerkrachaneekorn, Tanawat,Tankam, Theeranon,Sukwattanasinitt, Mongkol,Wacharasindhu, Sumrit
-
supporting information
(2021/04/15)
-
- 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)
-
- Extended Multicomponent Reactions with Indole Aldehydes: Access to Unprecedented Polyheterocyclic Scaffolds, Ligands of the Aryl Hydrocarbon Receptor
-
The participation of reactants undergoing a polarity inversion along a multicomponent reaction allows the continuation of the transformation with productive domino processes. Thus, indole aldehydes in Groebke–Blackburn–Bienaymé reactions lead to an initial adduct which spontaneously triggers a series of events leading to the discovery of novel reaction pathways together with direct access to a variety of linked, fused, and bridged polyheterocyclic scaffolds. Indole 3- and 4-carbaldehydes with suitable isocyanides and aminoazines afford fused adducts through oxidative Pictet–Spengler processes, whereas indole 2-carbaldehyde yields linked indolocarbazoles under mild conditions, and a bridged macrocycle at high temperature. These novel structures are potent activators of the human aryl hydrocarbon receptor signaling pathway.
- Ghashghaei, Ouldouz,Pedrola, Marina,Seghetti, Francesca,Martin, Victor V.,Zavarce, Ricardo,Babiak, Michal,Novacek, Jiri,Hartung, Frederick,Rolfes, Katharina M.,Haarmann-Stemmann, Thomas,Lavilla, Rodolfo
-
supporting information
p. 2603 - 2608
(2020/11/30)
-
- Direct Amidation of Esters by Ball Milling**
-
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
-
supporting information
p. 21868 - 21874
(2021/09/02)
-
- Diverse functionalization of aryl halides mediated by bis(phenylsulfonyl)methane
-
A palladium-catalyzed coupling reaction of bis(phenylsulfonyl)methane and aryl halides was developed. A variety of bis(phenylsulfonyl)methyl arenes were prepared in good yields. The transformations of bis(phenylsulfonyl)methyl to methyl, trideuteriomethyl, ethyl, carboxyl, and other functional groups were demonstrated. The results provided a new approach to diverse functionalization of aryl halides.
- Pan, Ping,Chen, Lei,Zhang, Xue-jing,Yan, Ming
-
-
- Visible light-mediated synthesis of amides from carboxylic acids and amine-boranes
-
Here, a photocatalytic deoxygenative amidation protocol using readily available amine-boranes and carboxylic acids is described. This approach features mild conditions, moderate-to-good yields, easy scale-up, and up to 62 examples of functionalized amides with diverse substituents. The synthetic robustness of this method was also demonstrated by its application in the late-stage functionalization of several pharmaceutical molecules.
- Chen, Xuenian,Kang, Jia-Xin,Ma, Yan-Na,Miao, Yu-Qi
-
supporting information
p. 3595 - 3599
(2021/06/06)
-
- Method for preparing amide from carboxylic acid under irradiation of blue light by taking iridium and cobalt complexes as catalysts
-
The invention relates to a method for preparing amide from carboxylic acid under the irradiation of blue light by taking iridium and cobalt complexes as catalysts, and belongs to the field of chemistry. The method comprises the following step of: by taking R substituted carboxylic acid and R1' and R2' substituted amines as raw materials, triphenylphosphine as a deoxidizing agent, [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 as a photocatalyst and Co(dmgH)(dmgH2)Cl2 as a metal complex catalyst, reacting in dichloromethane in an inert atmosphere and under the irradiation of blue light to obtain an amide compound, wherein R is an aryl group, a heteroaryl group, a protected amino group, a substituted alkyl group, a substituted aryl group or a substituted protected amino group, R1' is a hydrogen group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and R2' is a hydrogen group, a substituted alkyl group, a phenyl group or a substituted phenyl group.
- -
-
Paragraph 0033-0034
(2021/05/12)
-
- Visible-Light Photoredox-Catalyzed Amidation of Benzylic Alcohols
-
A new photocatalyzed route to amides from alcohols and amines mediated by visible light is presented. The reaction is carried out in ethyl acetate as a solvent. Ethyl acetate can be defined a green and bio-based solvent. The starting materials such as the energy source are easily available, stable, and inexpensive. The reaction has shown to be general and high yielding.
- Gaspa, Silvia,Farina, Andrea,Tilocca, Mariella,Porcheddu, Andrea,Pisano, Luisa,Carraro, Massimo,Azzena, Ugo,De Luca, Lidia
-
p. 11679 - 11687
(2020/10/23)
-
- Supramolecular Pd(II) complex of DPPF and dithiolate: An efficient catalyst for amino and phenoxycarbonylation using Co2(CO)8 as sustainable C1 source
-
Highly active, efficient and robust “dppf ligated tetranuclear palladium dithiolate complex” was synthesized and applied as a catalyst for chemical fixation of carbon monoxide for the synthesis value added chemicals such as tertiary amide and aromatic esters. The synthesized catalyst was characterized using different analytical techniques such as elemental analysis, 1H and 31P NMR spectroscopy. The use of Co2(CO)8 as a cheap, less toxic and low melting solid surrogate are additional advantages over the current protocol. The catalyst showed superior activity towards the Amino (10?3 mol % catalyst) and Phenoxycarbonylation (10-2 mol % catalyst) and high TON (104 to 103) and TOF (103 to 102 h-1). The Betol and Lintrin (active drug molecules) were synthesized under an optimized reaction condition. The scalability of the current protocol has been demonstrated up-to the gram level.
- Gaikwad, Vinayak V.,Mane, Pravin A.,Dey, Sandip,Patel, Divya,Bhanage, Bhalchandra M.
-
-
- Synthesis method of amide compound
-
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.
- -
-
Paragraph 0094-0095
(2020/09/09)
-
- Environmentally sustainable production and application of acyl phosphates
-
A versatile and environmentally friendly synthetic method for the formation of acyl phosphates is reported. By employing electrochemical oxidative dehydrogenative coupling, this transformation features a broad range of substrates, as well as metal-free, o
- Cai, Hu,Fu, Zhengjiang,Guo, Shengmei,Li, Sen,Liang, Zhibin,Yan, Wenjie
-
supporting information
p. 7343 - 7347
(2020/11/19)
-
- Two-step continuous flow synthesis of amide via oxidative amidation of methylarene
-
A green and efficient method for the synthesis of amides has been developed through oxidative amidation between methylarenes with amines in a two-step continuous flow system. This method integrates methylarene oxidation and amide formation into a single operation which is usually accomplished separately. Oxidation with tert-butyl hydroperoxide (TBHP) as “green” oxidant, the synthesis of amides under mild reaction conditions in continuous flow system and the utilization of methylarenes as starting material make this methodology novel and environment friendly. The practical value of this method is highlighted through the synthesis of high-profile pharmaceutical agents, acetylprocainamide.
- Fang, Zheng,Guo, Kai,He, Wei,Liu, Chengkou,Shi, Tingting,Yang, Yuhang,Yang, Zhao,Zhang, Zhimin
-
supporting information
(2020/02/28)
-
- Tandem Photoredox Catalysis: Enabling Carbonylative Amidation of Aryl and Alkylhalides
-
We report a new visible-light-mediated carbonylative amidation of aryl, heteroaryl, and alkyl halides. A tandem catalytic cycle of [Ir(ppy)2(dtb-bpy)]+ generates a potent iridium photoreductant through a second catalytic cycle in the presence of DIPEA, which productively engages aryl bromides, iodides, and even chlorides as well as primary, secondary, and tertiary alkyl iodides. The versatile in situ generated catalyst is compatible with aliphatic and aromatic amines, shows high functional-group tolerance, and enables the late-stage amidation of complex natural products.
- Connell, Timothy U.,Forni, José A.,Micic, Nenad,Polyzos, Anastasios,Weragoda, Geethika
-
supporting information
p. 18646 - 18654
(2020/08/21)
-
- Metal-Free C-N or C-C Bond Cleavages of α-Azido Ketones: An Oxidative-Amidation Strategy for the Synthesis of α-Ketothioamides and Amides
-
A novel metal-free oxidative-amidation strategy for the synthesis of α-ketothioamides and amides from α-azido ketones was developed. The C-H bond thionation of α-azido ketones with elemental sulfur could form α-ketothioacyl azide, which was then nucleophilically attacked by amines, causing the cleavage of the C-N bond to afford α-ketothioamides, while amides could be formed with the release of nitrogen gas and cyano anion in the presence of PhI(OAc)2 by selective C-C bond cleavage.
- Yu, Pei,Wang, Yuwei,Zeng, Zhigang,Chen, Yunfeng
-
p. 14883 - 14891
(2019/11/11)
-
- Metal-Free Transamidation of Secondary Amides by N-C Cleavage
-
Transamidation reactions represent a fundamental chemical process involving conversion of one amide functional group into another. Herein, we report a facile, highly chemoselective method for transamidation of N-tert-butoxycarbonylation (N-Boc) activated secondary amides that proceeds under exceedingly mild conditions in the absence of any additives. Because this reaction is performed in the absence of metals, oxidants, or reductants, the reaction tolerates a large number of useful functionalities. The reaction is compatible with diverse amides and nucleophilic amines, affording the transamidation products in excellent yields through direct nucleophilic addition to the amide bond. The utility of this methodology is highlighted in the synthesis of Tigan, a commercial antiemetic, directly from the amide bond. We expect that this new metal-free transamidation will have broad implications for the development of new transformations involving direct nucleophilic addition to the amide bond as a key step.
- Rahman, Md. Mahbubur,Li, Guangchen,Szostak, Michal
-
p. 12091 - 12100
(2019/10/11)
-
- PPh3/Selectfluor-Mediated Transformation of Carboxylic Acids into Acid Anhydrides and Acyl Fluorides and Its Application in Amide and Ester Synthesis
-
By taking the advantage of PPh3/Selectfluor system, carboxylic acids are efficiently converted into the pivotal intermediates acyloxyphosphonium ions that can selectively react with a second carboxylic acid or fluoride to in situ yield the corresponding acid anhydrides or acyl fluorides. The developed protocol features commercially availabile reagents, no involvement of base, room temperature conditions, and simple experimental procedure. Additionally, various amides or esters are readily achieved, respectively, with the addition of amines or alcohols.
- Yang, Zhen,Chen, Siwei,Yang, Fang,Zhang, Chenxi,Dou, You,Zhou, Qiuju,Yan, Yizhe,Tang, Lin
-
p. 5998 - 6002
(2019/08/21)
-
- Palladium-catalyzed carbonylation of aryl bromides using microwave heating and bis[CP-Fe(II)-(CO)2] as a carbon monoxide source
-
A palladium-catalyzed, microwave assisted carbonylative reaction is described for the synthesis of benzamides from aryl bromides and primary or secondary amines. The developed method uses bis(cyclopentadienyldicarbonyliron) as a solid source of carbon monoxide to produce a diverse set of secondary and tertiary amides in 42–82% yield.
- Roy, Tamal,Rydfjord, Jonas,S?vmarker, Jonas,Nordeman, Patrik
-
supporting information
p. 1230 - 1232
(2018/02/28)
-
- Versatile Heterogeneous Palladium Catalysts for Diverse Carbonylation Reactions under Atmospheric Carbon Monoxide Pressure
-
Herein, we report a versatile carbonylation protocol using heterogeneous Pd0 nanoparticles supported on the metal–organic frameworks (MOFs) MIL-88B-NH2 (Fe/Cr). The synthesis of a vast array of carbonyls, which includes amides, esters, carboxylic acids, and α-ketoamides, was achieved through mono- and dicarbonylation reactions. The selectivity could be controlled simply by tuning the reaction conditions. Superior activity and selectivity were recorded in some cases compared to that achieved with commercial Pd/C. However, the utility of an elaborate catalyst support is questionable and important reactivity and recyclability issues are discussed.
- Vico Solano, Marta,González Miera, Greco,Pascanu, Vlad,Inge, A. Ken,Martín-Matute, Belén
-
p. 1089 - 1095
(2018/02/06)
-
- An efficient procedure for chemoselective amidation from carboxylic acid and amine (ammonium salt) under mild conditions
-
Presented here is an efficient one-pot and catalyst-free procedure for the synthesis of amides starting from carboxylic acids and amine/ammonium salts using 2,2-dichloro-1,3-diisopropylimidazolidine-4,5-dione as the coupling agent. Reactions can proceed smoothly even with those bearing thermosensitive group(s) at ambient temperature, and the corresponding products of primary, secondary and tertiary amides can be afforded in moderate to excellent yields of up to 96%.
- Li, Jianhui,He, Shaopo,Fu, Haiqing,Chen, Xin,Tang, Min,Zhang, Dela,Wang, Bo
-
p. 2289 - 2303
(2017/12/26)
-
- Organic ligand-free carbonylation reactions with unsupported bulk Pd as catalyst
-
Herein, surprising results for bulk Pd-catalyzed carbonylation reactions are presented. Three types of carbonylation reactions can be realized efficiently under organic ligand-free conditions, namely, hydroaminocarbonylation of olefins, aminocarbonylation of aryl iodides and oxidative carbonylation of amines, which almost cover all the known mechanisms in carbonylation reactions. Notably, the bulk Pd catalyst system exhibited better catalytic activity than the classical homogeneous PdCl2/(2-OMePh)3P catalyst system. This study will create a momentous and new field of green carbonylation reactions.
- Liu, Shujuan,Wang, Hongli,Dai, Xingchao,Shi, Feng
-
supporting information
p. 3457 - 3462
(2018/08/06)
-
- Versatile palladium-catalyzed double carbonylation of aryl bromides
-
A versatile palladium-catalyzed double carbonylation of aryl bromides has been developed. Using Pd(OAc)2/BuPAd2 as the catalyst system and DBU as the base, under relatively low CO pressure, various α-ketoamides were produced in good
- Shen, Chaoren,Fink, Cornel,Laurenczy, Gabor,Dyson, Paul J.,Wu, Xiao-Feng
-
supporting information
p. 12422 - 12425
(2017/11/23)
-
- Palladium-Catalyzed Oxidative Carbonylation of Aryl Hydrazines with CO and O2 at Atmospheric Pressure
-
Palladium-catalyzed aerobic oxidative aminocarbonylation and alkoxycarbonylation reactions with aryl hydrazines as coupling partners have been developed. The oxidative carbonylation of aryl hydrazines proceeded smoothly at atmospheric pressure CO, employi
- Tu, Yongliang,Yuan, Lin,Wang, Tao,Wang, Changliu,Ke, Jiamei,Zhao, Junfeng
-
p. 4970 - 4976
(2017/05/12)
-
- Copper-catalyzed one-pot oxidative amidation between methylarenes and amines
-
A new method for the direct one-pot oxidative amidation between methylarenes and amines catalyzed by copper has been developed. This method integrates methylarene oxidation and amide bond formation, which are usually accomplished separately, into a single operation. In addition, the reaction provides a relatively high yield and has a wide substrate scope. Moreover, the starting reagents are abundant and available in a convenient way at a cheaper price.
- Yang, Yuhang,Gu, Jiajia,Fang, Zheng,Yang, Zhao,Wei, Ping,Guo, Kai
-
p. 22797 - 22801
(2017/07/10)
-
- Copper-catalyzed one-pot oxidative amidation of alcohol to amide via C-H activation
-
A one-pot oxidative amidation of both aliphatic and aromatic alcohols with N-chloramines, prepared in situ from many types of primary and secondary amines, was developed. This cross-coupling reaction integrates alcohol oxidation and amide bond formation, which are usually accomplished separately, into a single operation. And it was green, simple and convenient, which has a wide substrate scope and makes use of cheap, abundant, and easily available reagents. The practical value of this method is highlighted through the synthesis of a high-profile pharmaceutical agent, acetylprocainamide.
- Gu, Jiajia,Fang, Zheng,Yang, Yuhang,Yang, Zhao,Wan, Li,Li, Xin,Wei, Ping,Guo, Kai
-
p. 89413 - 89416
(2016/10/03)
-
- Palladium-catalyzed carbonylation of aryl halides: An efficient, heterogeneous and phosphine-free catalytic system for aminocarbonylation and alkoxycarbonylation employing Mo(CO)6 as a solid carbon monoxide source
-
Immobilized palladium metal-containing magnetic nanoparticles (ImmPd(0)-MNPs) were synthesized and characterized as an immobilized, phosphine-free catalyst for carbonylation reactions, namely the alkoxycarbonylation and aminocarbonylation reactions. Various substituted aryl iodides tolerated the reaction conditions and a wide variety of alcohols and amines were used efficiently. The effects of the solvent, base, and temperature were studied in both the mentioned reactions. The developed catalytic system avoids the use of phosphine ligands and can be reused for up to eight consecutive cycles. The recycled catalyst was characterized by TEM and ICP analysis.
- Hajipour, Abdol-Reza,Tavangar-Rizi, Zeinab,Iranpoor, Nasser
-
p. 78468 - 78476
(2016/09/09)
-
- Direct oxidative amination of aromatic aldehydes with amines in a continuous flow system using a metal-free catalyst
-
A novel method for metal-free oxidative amination of aromatic aldehydes and alcohols in the presence of H2O2/NaBr/H+ within 25 min in a continuous flow system has been developed. A series of different substrates were tested and the corresponding products were obtained in good yields .
- Gu, Jiajia,Fang, Zheng,Liu, Chengkou,Li, Xin,Wei, Ping,Guo, Kai
-
p. 72121 - 72126
(2016/08/09)
-
- CuCl/TBHP catalyzed synthesis of amides from aldehydes and amines in water
-
A CuCl/TBHP catalyzed amidation of aldehydes with amine under aqueous media is described. Both aliphatic and aromatic aldehydes coupled with a variety of amines under the reaction conditions employed.
- Lu, Shao-Yi,Badsara, Satpal Singh,Wu, Yi-Chun,Reddy, Daggula Mallikarjuna,Lee, Chin-Fa
-
supporting information
p. 633 - 636
(2016/01/26)
-
- Synthesis and characterization of bridged bis(amidato) rare earth metal amides and their applications in C-N bond formation reactions
-
Based on three bisamide proligands H2Ln (n = 1-3) (H2L1 = [(Me3C6H2CONHCH2)2CH2], H2L2 = [(Me3C6H2CONHCH2)2C(CH3)2], H2L3 = [Me3C6H2CONH(CH2)2]2NCH3), eight bis(amidato) trivalent rare-earth metal amides {LnRE[N(TMS)2]}2 (n = 1, RE = La (1), Sm (2), Nd (3), Y (4); n = 2, RE = La (5), Nd (6); n = 3, RE = La (7), Nd (8); TMS = SiMe3) were successfully synthesized by treatment of H2Ln with RE[N(TMS)2]3 in a 1:1 molar ratio. Complexes 3, and 5-8 were characterized by single-crystal X-ray diffraction, and NMR characterization was carried out for the La complexes 1, 5, 7 and the Y complex 4. These complexes exhibited high catalytic activities in both the direct amidation of aldehydes and the addition of amines with carbodiimine. It was found that the bis(amidato) rare earth metal amides bearing different linkers have different effects on the transformations and lanthanum and neodymium complexes performed better than others.
- Zhao, Bei,Xiao, Yang,Yuan, Dan,Lu, Chengrong,Yao, Yingming
-
p. 3880 - 3887
(2016/03/05)
-
- Covalent triazine framework-supported palladium as a ligand-free catalyst for the selective double carbonylation of aryl iodides under ambient pressure of CO
-
Carbonylation of aryl iodides with amines under atmospheric pressure of CO, catalyzed by Pd/CTFs (covalent triazine frameworks) without any specific additives, leads to the highly selective synthesis of α-ketoamides.
- Wang, Zhifang,Liu, Cuibo,Huang, Yi,Hu, Yuchen,Zhang, Bin
-
supporting information
p. 2960 - 2963
(2016/02/19)
-
- Copper-catalyzed and iodide-promoted aerobic C-C bond cleavage/C-N bond formation toward the synthesis of amides
-
A copper-catalyzed and iodide-promoted aerobic C-C bond cleavage/C-N bond formation reaction between ketone and simple amine was developed toward the synthesis of amides, which are useful synthetic intermediates in organic synthesis and important skeletons of biologically active molecules. Notably, the reaction conditions are very mild, and preliminary mechanistic investigations indicate that molecular oxygen might be involved in the C-C bond cleavage process.
- Wu, Kun,Huang, Zhiliang,Ma, Yiyang,Lei, Aiwen
-
p. 24349 - 24352
(2016/03/15)
-
- Stable and Reusable Binaphthyl-Supported Palladium Catalyst for Aminocarbonylation of Aryl Iodides
-
A binaphthyl-supported Pd nanoparticles (Pd-BNP)-catalyzed aminocarbonylation of aryl iodides in the presence of carbon monoxide and amines for the synthesis of amides has been developed. This methodology provides an efficient route for the synthesis of a COX-2 enzyme inhibitor having anti-inflammatory activity.
- Sharma, Nidhi,Sekar, Govindasamy
-
supporting information
p. 314 - 320
(2016/02/14)
-
- Direct oxidative amidation between methylarenes and amines in water
-
An environmentally friendly direct oxidative amidation between methylarenes and free amines was developed. The aromatic amide could be prepared efficiently from raw chemicals by employing TBHP as a "green" oxidant with co-catalysis of TBAI and FeCl3 in water.
- Wang, Tao,Yuan, Lin,Zhao, Zhenguang,Shao, Ailong,Gao, Meng,Huang, Yangfei,Xiong, Fei,Zhang, Huali,Zhao, Junfeng
-
supporting information
p. 2741 - 2744
(2015/05/27)
-
- A two-step continuous flow synthesis of amides from alcohol using a metal-free catalyst
-
Metal-free oxidative amination of aromatic alcohols in the presence of TBHP provides convenient access to amides in 86-96% yield under mild reaction conditions within 15 min in a two-step continuous flow reactor system. This method avoids expensive transition metal catalysts and integrates alcohol oxidation and amide bond formation, which are usually accomplished separately, into a single operation.
- Gu, Jiajia,Fang, Zheng,Liu, Chengkou,Yang, Zhao,Li, Xin,Wei, Ping,Guo, Kai
-
p. 95014 - 95019
(2015/11/24)
-
- Size of gold nanoparticles driving selective amide synthesis through aerobic condensation of aldehydes and amines
-
Metal nanoparticles (NPs) have attracted much attention in many fields due to their intrinsic characteristics. It is generally accepted that smaller NPs (1.5-3 nm) are more active than larger NPs, and reverse cases are very rare. We report here the direct aerobic oxidative amide synthesis from aldehydes and amines catalyzed by polymer-incarcerated gold (Au) NPs. A unique correlation between imine/amide selectivity and size of NPs was discovered; Au-NPs of medium size (4.5-11 nm) were found to be optimal. High yields were obtained with a broad range of substrates, including primary amines. Au-NPs of medium size could be recovered and reused several times without loss of activity, and they showed good activity and selectivity in amide formation from alcohols and amines. Superior activity and selectivity of gold nanoparticles (Au-NPs) of medium size (4.5-11 nm) were found for the direct and selective aerobic oxidative amide synthesis from various combinations of aldehydes and amines. This is an example of an unusual correlation between the size of NPs and their activity/selectivity. These catalysts could be recovered and reused several times without loss of activity.
- Miyamura, Hiroyuki,Min, Hyemin,Soulé, Jean-Fran?ois,Kobayashi, Shu
-
supporting information
p. 7564 - 7567
(2015/06/25)
-
- 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)
-
- Room-Temperature Decarboxylative Couplings of α-Oxocarboxylates with Aryl Halides by Merging Photoredox with Palladium Catalysis
-
Enabled by merging iridium photoredox catalysis and palladium catalysis, α-oxocarboxylate salts can be decarboxylatively coupled with aryl halides to generate aromatic ketones and amides at room temperature. DFT calculations suggest that this reaction proceeds through a Pd0-PdII-PdIII pathway, in which the PdIII intermediate is responsible for reoxidizing IrII to complete the IrIII-IrIII-IrII photoredox cycle. Like a mergin': Enabled by merging iridium photoredox catalysis and palladium catalysis, palladium-catalyzed decarboxylative coupling of α-oxocarboxylates with aryl halides can proceed at room temperature. DFT calculations suggest that a Pd0-PdII-PdIII catalytic cycle is merged with an IrIII-IrIII-IrII photoredox cycle, in which PdIII is responsible for oxidizing IrII to complete the photoredox cycle.
- Cheng, Wan-Min,Shang, Rui,Yu, Hai-Zhu,Fu, Yao
-
supporting information
p. 13191 - 13195
(2015/09/15)
-
- N2 extrusion and co insertion: A novel palladium-catalyzed carbonylative transformation of aryltriazenes
-
A novel procedure for the replacement of N2 with CO of aryltriazenes has been developed. Aryltriazenes were converted to the corresponding arylamides catalyzed by 1 mol % of PdCl2/P(o-Tol)3 under CO pressure. In this process, aryldiazonium salts were generated in the presence of 40 mol % of MeSO3H. Nitrogen was released from the substrates and CO formally inserted. Aryl bromides, iodides, alkynes, and free hydroxyl groups can be tolerated in this transformation.
- Li, Wanfang,Wu, Xiao-Feng
-
p. 1910 - 1913
(2015/04/27)
-
- Photoinduced Aminocarbonylation of Aryl Iodides
-
Transition metal-catalyzed aminocarbonylation of aryl halides with CO and amines, pioneered by Heck and co-workers in the 1970s, is among the most commonly employed reactions to make aromatic amides. A catalyst-free aminocarbonylation of aryl iodides with CO and amines, which simply uses photoirradiation conditions by Xe-lamp, has now been developed. This methodology shows broad functional-group tolerance, including that of heteroaromatic amides. A hybrid radical/ionic chain mechanism, involving electron transfer from zwitterionic radical intermediates generated by nucleophilic attack of amines to aroyl radicals, is proposed.
- Kawamoto, Takuji,Sato, Aoi,Ryu, Ilhyong
-
supporting information
p. 14764 - 14767
(2015/10/19)
-
- Co2(CO)8 as a convenient in situ CO source for the direct synthesis of benzamides from aryl halides (Br/I) via aminocarbonylation
-
A fast, mild, and functional group tolerant method for the direct synthesis of benzamides from aryl halides (Br, I) via aminocarbonylation, using solid Co2(CO)8 as a convenient CO source, has been demonstrated. The developed method is applicable to a wide variety of 1 and cyclic and acyclic 2 amines. Nitro substituted (o, m and p) aryl halides have easily been converted to the corresponding benzamides, without the reduction of the nitro group, in high yields using this in situ carbonylation methodology under microwave irradiation.
- Baburajan, Poongavanam,Elango, Kuppanagounder P.
-
supporting information
p. 1006 - 1010
(2014/02/14)
-
- Co2(CO)8 as a convenient in situ CO source for the direct synthesis of benzamides from aryl halides (Br/I) via aminocarbonylation
-
A fast, mild, and functional group tolerant method for the direct synthesis of benzamides from aryl halides (Br, I) via aminocarbonylation, using solid Co2(CO)8 as a convenient CO source, has been demonstrated. The developed method is applicable to a wide variety of 1° and cyclic and acyclic 2°amines. Nitro substituted (o, m and p) aryl halides have easily been converted to the corresponding benzamides, without the reduction of the nitro group, in high yields using this in situ carbonylation methodology under microwave irradiation.
- Baburajan, Poongavanam,Elango, Kuppanagounder P.
-
supporting information
p. 1006 - 1010
(2015/02/19)
-
- Tuning reductive and oxidative photoinduced electron transfer in amide-linked anthraquinone-porphyrin-ferrocene architectures
-
Porphyrin amino acids 3a-3h with meso substituents Ar of tunable electron-donating power (Ar = 4-C6H4OnBu, 4-C6H4OMe, 4-C6H4Me, Mes, C6H5, 4-C6H4F, 4-C6H4CF3, C6F5) have been linked at the N terminus to anthraquinone Q as electron acceptor through amide bonds to give Q-PAr dyads 4a-4h. These were conjugated to ferrocene Fc at the C terminus as electron donor to give the acceptor-chromophore-donor Q-PAr-Fc triads 6a-6h. To further modify the energies of the electronically excited and charge-separated states, the triads 6a-6h were metallated with zinc(II) to give the corresponding Q-(Zn)PAr-Fc triads Zn-6a-Zn-6h. The Q-PAr1 dyad (Ar1 = C6H5) was further extended with a second porphyrin PAr2 (Ar2 = 4-C6H4Me) as well as appended to a ferrocene to give the tetrad Q-PAr1-PAr2-Fc 9. Almost all the conjugates show strongly reduced fluorescence quantum yields and excited-state lifetimes, which has been interpreted as photoinduced electron transfer (PET) either from the excited porphyrin to the quinone (oxidative PET) or from the ferrocene to the excited porphyrin (reductive PET). Electrochemical data, absorption spectroscopy, steady-state emission, time-resolved fluorescence, transient absorption pump-probe spectroscopy as well as DFT calculations have been used to elaborate the preferred PET pathway (reductive vs. oxidative PET) in these architectures with systematically varied electron-donating substituents at the central chromophore. The initial photoinduced electron transfer (PET) in anthraquinone-(porphyrinAr)n-ferrocenes (n = 1, 2) is modulated by the HOMO and LUMO levels of the porphyrin chromophores by meso substituent effects. Electrochemical and spectroscopic data as well as DFT calculations were used to elaborate the preferred PET pathway in these architectures with different electron donation on the porphyrin.
- Melomedov, Jascha,Ochsmann, Julian Robert,Meister, Michael,Laquai, Frédéric,Heinze, Katja
-
supporting information
p. 1984 - 2001
(2015/04/27)
-
- Mild and direct conversion of esters to morpholine amides using diisobutyl(morpholino)aluminum: Application to efficient one-pot synthesis of ketones and aldehydes from esters
-
Morpholine amide intermediates, which are easily prepared by aminolysis of various esters with diisobutyl(morpholino)aluminum, react with organolithium and reducing agents (DIBALH or LDBMA) without isolation of the aminolysis intermediates to give ketones in 83-95% yields and aldehydes quantitatively.
- Jeon, Ah Ram,Kim, Min Eai,Park, Jae Kyo,Shin, Won Kyu,An, Duk Keun
-
p. 4420 - 4424
(2014/06/10)
-
- Visible light induced photocatalytic conversion of enamines into amides
-
A series of enamines were photocatalytically cleaved to produce amide products under simple visible-light irradiation from a 45 W household light bulb. Mechanistically, the reactions appear to involve photosensitized formation of a singlet oxygen intermediate and a subsequent [2+2] cycloaddition event. Georg Thieme Verlag Stuttgart, New York.
- Li, Jing,Cai, Shunyou,Chen, Jietao,Zhao, Yaohong,Wang, David Zhigang
-
p. 1626 - 1628
(2014/07/08)
-
- Tuning reductive and oxidative photoinduced electron transfer in amide-linked anthraquinone-porphyrin-ferrocene architectures
-
Porphyrin amino acids 3a-3h with meso substituents Ar of tunable electron-donating power (Ar = 4-C6H4OnBu, 4-C 6H4OMe, 4-C6H4Me, Mes, C 6H5, 4-C6H4F, 4-C6H 4CF3, C6F5) have been linked at the N terminus to anthraquinone Q as electron acceptor through amide bonds to give Q-PAr dyads 4a-4h. These were conjugated to ferrocene Fc at the C terminus as electron donor to give the acceptor-chromophore-donor Q-P Ar-Fc triads 6a-6h. To further modify the energies of the electronically excited and charge-separated states, the triads 6a-6h were metallated with zinc(II) to give the corresponding Q-(Zn)PAr-Fc triads Zn-6a-Zn-6h. The Q-PAr1 dyad (Ar1 = C 6H5) was further extended with a second porphyrin P Ar2 (Ar2 = 4-C6H4Me) as well as appended to a ferrocene to give the tetrad Q-PAr1-PAr2-Fc 9. Almost all the conjugates show strongly reduced fluorescence quantum yields and excited-state lifetimes, which has been interpreted as photoinduced electron transfer (PET) either from the excited porphyrin to the quinone (oxidative PET) or from the ferrocene to the excited porphyrin (reductive PET). Electrochemical data, absorption spectroscopy, steady-state emission, time-resolved fluorescence, transient absorption pump-probe spectroscopy as well as DFT calculations have been used to elaborate the preferred PET pathway (reductive vs. oxidative PET) in these architectures with systematically varied electron-donating substituents at the central chromophore. Copyright
- Melomedov, Jascha,Ochsmann, Julian Robert,Meister, Michael,Laquai, Frédéric,Heinze, Katja
-
supporting information
p. 1984 - 2001
(2014/05/06)
-
- AIBN-initiated metal free amidation of aldehydes using N-chloroamines
-
An efficient and environmentally benign amidation of aldehydes with N-chloroamines has been developed using AIBN as an initiator. This methodology offers a metal free and base free approach and is endowed with mild reaction conditions, high yields, and good functional group tolerance.
- Vanjari, Rajeshwer,Guntreddi, Tirumaleswararao,Singh, Krishna Nand
-
supporting information
p. 351 - 356
(2014/01/06)
-
- Polymer supported Pd catalyzed carbonylation of aryl bromides for the synthesis of aryl esters and amides
-
A polymer-anchored palladium(ii) catalyst was synthesized and characterized using various spectroscopic techniques. Its catalytic activity was evaluated for the alkoxycarbonylation and aminocarbonylation reactions. These carbonylation reactions were carried out for various substituted aryl bromides using alcohols and amines. Both the reactions were optimized by varying the bases, temperature and solvents. These experiments were carried out under high CO pressure. The catalyst was very stable and can be facilely recovered and reused six times without a significant decrease in its activity and selectivity. the Partner Organisations 2014.
- Islam, Sk Manirul,Ghosh, Kajari,Roy, Anupam Singha,Molla, Rostam Ali
-
p. 38986 - 38999
(2014/11/07)
-
