- Synthesis of Benzoisoselenazolones via Rh(III)-Catalyzed Direct Annulative Selenation by Using Elemental Selenium
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Isoselenazolone derivatives have attracted significant research interest because of their potent therapeutic activities and indispensable applications in organic synthesis. Efficient construction of functionalized isoselenazolone scaffolds is still challenging, and thus new synthetic approaches with improved operational simplicity have been of particular interest. In this manuscript, we introduce a rhodium-catalyzed direct selenium annulation by using stable and tractable elemental selenium. A series of benzamides as well as acrylamides were successfully coupled with selenium under mild reaction conditions, and the obtained isoselenazolones could be pivotal synthetic precursors for several organoselenium compounds. Based on the designed control experiments and X-ray absorption spectroscopy measurements, we propose an unprecedented selenation mechanism involving a highly electrophilic Se(IV) species as the reactive selenium donor. The reaction mechanism was further verified by a computational study.
- Xu-Xu, Qing-Feng,Nishii, Yuji,Uetake, Yuta,Sakurai, Hidehiro,Miura, Masahiro
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supporting information
p. 17952 - 17959
(2021/11/16)
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- Convenient synthesis of benziodazolone: New reagents for direct esterification of alcohols and amidation of amines
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Hypervalent iodine heterocycles represent one of the important classes of hypervalent iodine reagents with many applications in organic synthesis. This paper reports a simple and convenient synthesis of benziodazolones by the reaction of readily available iodobenzamides with m-chloroperoxybenzoic acid in acetonitrile at room temperature. The structure of one of these new iodine heterocycles was confirmed by X-ray analysis. In combination with PPh3 and pyridine, these benziodazolones can smoothly react with alcohols or amines to produce the corresponding esters or amides of 3-chlorobenzoic acid, respectively. It was found that the novel benziodazolone reagent reacts more efficiently than the analogous benziodoxolone reagent in this esterification.
- Postnikov, Pavel S.,Rohde, Gregory T.,Saito, Akio,Shea, Michael T.,Vlasenko, Yulia A.,Yoshimura, Akira,Yusubov, Mekhman S.,Zhdankin, Viktor V.
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- Mechanochemical Transformation of CF3 Group: Synthesis of Amides and Schiff Bases
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We communicate two mild, solvent-free mechanochemical coupling transformations of CF3 group with nitro compounds into amides or Schiff bases employing Ytterbia as a catalyst. This process proceeds via C?F bond activation, accompanied with utilisation of Si-based reductants/oxygen scavengers – reductants of the nitro group. The scope and limitations of the disclosed methodologies are thoroughly studied. To the best of our knowledge, this work is the first example of mechanical energy promoted transformation of the inert CF3 group into other functionalities. (Figure presented.).
- Mkrtchyan, Satenik,Jakubczyk, Micha?,Lanka, Suneel,Yar, Muhammad,Ayub, Khurshid,Shkoor, Mohanad,Pittelkow, Michael,Iaroshenko, Viktor O.
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supporting information
p. 5448 - 5460
(2021/10/19)
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- Cu-catalyzed arylation of bromo-difluoro-acetamides by aryl boronic acids, aryl trialkoxysilanes and dimethyl-aryl-sulfonium salts: New entries to aromatic amides
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We describe a mechanism-guided discovery of a synthetic methodology that enables the preparation of aromatic amides from 2-bromo-2, 2-difluoroacetamides utilizing a copper-catalyzed direct arylation. Readily available and structurally simple aryl precursors such as aryl boronic acids, aryl trialkoxysilanes and dimethyl-aryl-sulfonium salts were used as the source for the aryl substituents. The scope of the reactions was tested, and the reactions were insensitive to the electronic nature of the aryl groups, as both electron-rich and electron-deficient aryls were successfully introduced. A wide range of 2-bromo-2, 2-difluoroacetamides as either aliphatic or aromatic secondary or tertiary amides were also reactive under the developed conditions. The described synthetic protocols displayed excellent efficiency and were successfully utilized for the expeditious preparation of diverse aromatic amides in good-to-excellent yields. The reactions were scaled up to gram quantities.
- Iaroshenko, Viktor O.,Jakubczyk, Micha?,Lanka, Suneel,Mkrtchyan, Satenik,Pittelkow, Michael
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- An unprecedented cobalt-catalyzed selective aroylation of primary amines with aroyl peroxides
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A novel and facile cobalt-catalyzed selective aroylation of primary amines with aroyl peroxides was developed for the synthesis of aryl amides. It was unprecedented that C[sbnd]N bond formation product was selectively generated without the common N[sbnd]O bond formation product. Aroyl peroxides act as the sole aroylation reagent without additional base or oxidant. The reactions proceeded under mild conditions and showed broad substrates scope with a series of primary amines and aroyl peroxides.
- Li, Dong,Li, Jiale,Li, Juanjuan,Yuan, Songdong,Zhang, Qian
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supporting information
(2020/09/16)
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- Design and synthesis of arylamidine derivatives as serotonin/norepinephrine dual reuptake inhibitors
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To improve the in vivo antidepressant activity of previously reported serotonin (5-HT) and norepinephrine (NE) dual reuptake inhibitors, three series of arylamidine derivatives were designed and synthesized. The in vitro 5-HT and NE reuptake inhibitory activities of these compounds were evaluated, and compound II-5 was identified as the most potent 5-HT (IC50 = 620 nM) and NE (IC50 = 10 nM) dual reuptake inhibitor. Compound II-5 exhibited potent antidepressant activity in the rat tail suspension test and showed an acceptable safety profile in a preliminary acute toxicity test in mice. Our results show that these arylamidine derivatives exhibit potent 5-HT/NE dual reuptake inhibition and should be explored further as antidepressant drug candidates.
- Wen, Hui,Qin, Wen,Yang, Guangzhong,Guo, Yanshen
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- Hydrogen Bond Directed ortho-Selective C?H Borylation of Secondary Aromatic Amides
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Reported is an iridium catalyst for ortho-selective C?H borylation of challenging secondary aromatic amide substrates, and the regioselectivity is controlled by hydrogen-bond interactions. The BAIPy-Ir catalyst forms three hydrogen bonds with the substrate during the crucial activation step, and allows ortho-C?H borylation with high selectivity. The catalyst displays unprecedented ortho selectivities for a wide variety of substrates that differ in electronic and steric properties, and the catalyst tolerates various functional groups. The regioselective C?H borylation catalyst is readily accessible and converts substrates on gram scale with high selectivity and conversion.
- Bai, Shao-Tao,Bheeter, Charles B.,Reek, Joost N. H.
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supporting information
p. 13039 - 13043
(2019/07/31)
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- A Practical and General Amidation Method from Isocyanates Enabled by Flow Technology
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The addition of carbon nucleophiles to isocyanates represents a conceptually flexible and efficient approach to the preparation of amides. This general synthetic strategy has, however, been relatively underutilized owing to narrow substrate tolerance and the requirement for less favourable reaction conditions. Herein, we disclose a high-yielding, mass-efficient, and scalable method with appreciable functional group tolerance for the formation of amides by reaction of Grignard reagents with isocyanates. Through the application of flow chemistry and the use of substoichiometric amounts of CuBr2, this process has been developed to encompass a broad range of substrates, including reactants found to be incompatible with previously published procedures.
- Williams, Jason D.,Kerr, William J.,Leach, Stuart G.,Lindsay, David M.
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supporting information
p. 12126 - 12130
(2018/09/11)
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- Amidation and esterification of carboxylic acids with amines and phenols by N,N′-diisopropylcarbodiimide: A new approach for amide and ester bond formation in water
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The present study reports the successful synthesis of two important and abundant functional groups “ester and amide” by N,N′-diisopropylcarbodiimide (DIC) in water as a green solvent. A wide range of substrates could be employed with high functional group tolerance. The products were obtained in high yields after short reaction times. This method provides an efficient, economic, simple and very mild protocol for ester and amide bond formation in aqueous media. In addition, this work not only may lead to environmentally benign systems but also will provide a new aspect of organic chemistry in water.
- Fattahi, Nadia,Ayubi, Morteza,Ramazani, Ali
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p. 4351 - 4356
(2018/07/13)
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- Palladium-Catalyzed Direct Synthesis of Phenanthridones from Benzamides through Tandem N–H/C–H Arylation
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We report a palladium-catalyzed method for the direct synthesis of phenanthridones from benzamides in a single step. Unlike previous reports, the current protocol does not need any directing groups or any harsh conditions. This methodology has a wide functional group tolerance therefore a series of phenanthridones were synthesized with a yield up to 87 %. The efficacy of this protocol was further explored by synthesizing some important naturally occurring amaryllidaceae alkaloids in a single step with very good yields.
- Banerji, Biswadip,Chatterjee, Satadru,Chandrasekhar,Nayan, Chinmay,Killi, Sunil Kumar
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supporting information
p. 5214 - 5218
(2017/09/29)
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- Pathways in the Degradation of Geminal Diazides
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The degradation of geminal diazides is described. We show that diazido acetates are converted into tetrazoles through the treatment with bases. The reaction of dichloro ketones with azide anions provides acyl azides, through in situ formation of diazido ketones. We present experimental and theoretical evidence that both fragmentations may involve the generation of acyl cyanide intermediates. The controlled degradation of terminal alkynes into amides (by loss of one carbon) or ureas (by loss of two carbons) is also shown.
- Holzschneider, Kristina,H?ring, Andreas P.,Haack, Alexander,Corey, Daniel J.,Benter, Thorsten,Kirsch, Stefan F.
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p. 8242 - 8250
(2017/08/14)
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- Copper-Catalyzed Ligand-Free Amidation of Benzylic Hydrocarbons and Inactive Aliphatic Alkanes
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An efficient copper-catalyzed amidation of benzylic hydrocarbons and inactive aliphatic alkanes with simple amides was developed. The protocol proceeded smoothly without any ligand, and a wide range of N-alkylated aromatic and aliphatic amides, sulfonamides, and imides were synthesized in good yields.
- Zeng, Hui-Ting,Huang, Jing-Mei
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supporting information
p. 4276 - 4279
(2015/09/15)
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- Polymer supported Pd catalyzed carbonylation of aryl bromides for the synthesis of aryl esters and amides
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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
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p. 38986 - 38999
(2014/11/07)
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- The α-effect in hydrazinolysis of 4-chloro-2-nitrophenyl x-substituted-benzoates: Effect of substituent x on reaction mechanism and the α-effect
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Second-order rate constants (kN) have been measured spectrophotometrically for the reaction of 4-chloro-2- nitrophenyl X-substituted-benzoates (6a-6h) with a series of primary amines including hydrazine in 80 mol % H2O/20 mol % DMSO at 25.0°C. The Bronsted-type plot for the reaction of 4-chloro-2-nitrophenyl benzoate (6d) is linear with βnuc = 0.74 when hydrazine is excluded from the correlation. Such a linear Bronsted-type plot is typical for reactions reported previously to proceed through a stepwise mechanism in which expulsion of the leaving group occurs in the rate-determining step (RDS). The Hammett plots for the reactions of 6a-6h with hydrazine and glycylglycine are nonlinear. In contrast, the Yukawa-Tsuno plots exhibit excellent linear correlations with ?X = 1.29-1.45 and r = 0.53-0.56, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by resonance stabilization of the substrates possessing an electron-donating group (EDG). Hydrazine is ca. 47-93 times more reactive than similarly basic glycylglycine toward 6a-6h (e.g., the α-effect). The α-effect increases as the substituent X in the benzoyl moiety becomes a stronger electronwithdrawing group (EWG), indicating that destabilization of the ground state (GS) of hydrazine through the repulsion between the nonbonding electron pairs on the two N atoms is not solely responsible for the substituent-dependent α-effect. Stabilization of transition state (TS) through five-membered cyclic TSs, which would increase the electrophilicity of the reaction center or the nucleofugality of the leaving group, contributes to the α-effect observed in this study.
- Kim, Min-Young,Kim, Tae-Eun,Lee, Jieun,Um, Ik-Hwan
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p. 2271 - 2276
(2014/09/29)
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- AIBN-initiated metal free amidation of aldehydes using N-chloroamines
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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
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supporting information
p. 351 - 356
(2014/01/06)
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- Direct amidation from alcohols and amines through a tandem oxidation process catalyzed by heterogeneous-polymer-incarcerated gold nanoparticles under aerobic conditions
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We describe herein a highly elegant and suitable synthesis of amide products from alcohols and amines through a tandem oxidation process that uses molecular oxygen as a terminal oxidant. Carbon-black-stabilized polymer-incarcerated gold (PICB-Au) or gold/cobalt (PICB-Au/Co) nanoparticles were employed as an efficient heterogeneous catalyst depending on alcohol reactivity and generated only water as the major co-product of the reaction. A wide scope of substrate applicability was shown with 42 examples. The catalysts could be recovered and reused without loss of activity by using a simple operation. Gold standard: A highly efficient green method for amide synthesis from alcohols and amines catalyzed by gold nanoparticles stabilized by styrene-based copolymers has been developed (see scheme). Two catalysts have been used with high selectivity depending on the combination of substrates. These Au nanoparticle catalysts can be recovered and reused several times by simple operations. Copyright
- Soule, Jean-Francois,Miyamura, Hiroyuki,Kobayashi, Shu
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supporting information
p. 2614 - 2626
(2013/11/19)
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- Mild and rapid Pd-catalyzed cross-coupling with hydrazine in continuous flow: Application to the synthesis of functionalized heterocycles
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Minimizing risk: The synthesis of arylhydrazines through C?£?N cross-coupling of aryl chlorides with hydrazine is described. Through the use of continuous flow, the hazards associated with the use of hydrazine in the presence of transition metals are decreased. In addition, multistep flow sequences have also been developed for the generation of functionalized heterocycles utilizing the arylhydrazine intermediates.
- Deangelis, Andrew,Wang, Dong-Hui,Buchwald, Stephen L.
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supporting information
p. 3434 - 3437
(2013/05/09)
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- MnO2 promoted sequential C-O and C-N bond formation via C-H activation of methylarenes: A new approach to amides
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A novel and efficient approach for the synthesis of amides has been developed through manganese dioxide promoted nondirected C-H activation of methylarenes under mild reaction conditions employing N-chloroamines as effective coupling partners.
- Vanjari, Rajeshwer,Guntreddi, Tirumaleswararao,Singh, Krishna Nand
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supporting information
p. 4908 - 4911
(2013/10/08)
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- Catalytic acylation of amines with aldehydes or aldoximes
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The simple nickel salt NiCl2?6H2O catalyzes the coupling of aldoximes with amines to give secondary or tertiary amide products. The aldoxime can be prepared in situ from the corresponding aldehyde. The use of 18O-labeled oximes has allowed insight into the mechanism of this reaction.
- Allen, C. Liana,Davulcu, Simge,Williams, Jonathan M. J.
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supporting information; experimental part
p. 5096 - 5099
(2011/02/21)
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- Molybdenum-mediated carbonylation of aryl halides with nucleophiles using microwave irradiation
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Figure Presented. A new, efficient, and practical molybdenum-mediated carbonylation of aryl and heteroaryl halides with a variety of nucleophiles is described using microwave irradiation. A range of reactions illustrating the wide scope of this chemistry were carried out and proceeded in good to excellent yields.
- Roberts, Bryan,Liptrot, David,Alcaraz, Lilian,Luker, Tim,Stocks, Michael J.
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supporting information; experimental part
p. 4280 - 4283
(2010/11/04)
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- Oxidative amidation and azidation of aldehydes by NHC catalysis
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Figure presented N-Heterocyclic carbene catalyzed oxidative amidations of various aldehydes to the corresponding hexafluoroisopropylesters by using the readily available organic oxidant A are described. The hexafluoroisopropylesters prepared in situ are shown to be highly useful active esters for amide bond formation. In addition, oxidative azidation of aldehydes is presented. These mild organocatalytic processes do not use any transition metal.
- De Sarkar, Suman,Studer, Armido
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supporting information; experimental part
p. 1992 - 1995
(2010/07/10)
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- Expedient synthesis of secondary amines bound to indole resin and cleavage of resin-bound urea, amide and sulfonamide under mild conditions
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Highly efficient, new protocols for the attachment of primary amines to indole aldehyde resin using Ti(OiPr)4-NaBH4 and CH(OMe)3-NaBH3CN-HOAc are reported. Mild cleavage conditions for the release of urea, amide and sulfonamide products from the solid support using 1% trifluoroacetic acid (TFA) are developed.
- Bhattacharyya, Sukanta,Gooding, Owen W.,Labadie, Jeff
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p. 6099 - 6102
(2007/10/03)
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- Versatile Acylation of N-Nucleophiles Using a New Polymer-Supported 1-Hydroxybenzotriazole Derivative
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The synthesis of a new polymer-supported coupling reagent derived from 1-hydroxybenzotriazole is described. An aminomethylated polystyrene was functionalized by reaction with 3-nitro-4- chlorobenzenesulfonyl chloride (2) followed by treatement with hydrazine hydrate, to give the polymeric N-benzyl-1-hydroxybenzotriazole-6-sulfonamide (4).The polymeric reagent 4 was shown to be highly efficient for the synthesis of amides. The efficiency of 4 could be attributed to its high acidity, conferred by the sulfonyl moiety. The procedure for amide synthesis involves the formation of an activated ester on the derivatized polymer followed, in a second step, by treatment with an amine to generate the amide in solution. Simple filtration allows the separation of the product from the polymeric reagent which in this case plays the role of leaving group. An optimization study of this two-step procedure was performed. As amides are obtained in solution free of reaction byproducts, this method can be used in an automated procedure to recover them directly into a 96 well plate, ready to be used in high throughput screening assays. Thus 4 was shown to be particularly suitable for the high throughput parallel synthesis of amides libraries.
- Pop, Iuliana E.,Déprez, Beno?t P.,Tartar, André L.
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p. 2594 - 2603
(2007/10/03)
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- Potential Central Nervous System Active Agents. 1. Synthesis of Aromatic N-Benzyl Amides
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The preparation and spectral properties (IR, MS, NMR) are given for 18 aromatic N-benzyl amides, variously substituted on the acyl part, including four new ones and an (E)-cinnamide derivative.The amides were prepared by heating the appropriate N-benzylammonium salt in o-xylene, or from the reaction of the corresponding acid chloride with benzylamine.The occurrence of an intense peak in their mass spectra, which corresponds to the loss of the N-acyl substituent without hydrogen transfer, is reported.
- Agwada, Vincent C.
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p. 479 - 481
(2007/10/02)
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