- Electrochemical Benzylic C-H Functionalization with Isocyanides
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We report the challenging direct carbamoylation or cyanation of benzylic C(sp3)-H bonds with an isocyanide via an electrochemical process giving rise to structures that are encountered in several biologically relevant compounds and drugs. This transformation proceeds under mild conditions without the need for any external oxidant and avoids the necessity to start from a prefunctionalized benzylic substrate or the deployment of the cation pool method. The anodic oxidation of the benzylic position and the subsequent addition of the isocyanide lead to the formation of a C-C bond and to a nitrilium cation that hydrolyzes to yield α-Aryl acetamide derivatives, whereas the elimination of a t-butyl cation delivers α-Aryl acetonitrile derivatives.
- Grimaud, Laurence,Guillot, Régis,Tang, Shanyu,Vincent, Guillaume,Vitale, Maxime R.
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supporting information
p. 2125 - 2130
(2022/04/07)
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- Weak base-promoted selective rearrangement of oxaziridines to amidesviavisible-light photoredox catalysis
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The selective rearrangement of oxaziridines to amidesviaa single electron transfer (SET) pathway is unexplored. In this study, we present a weak base-promoted selective rearrangement of oxaziridines to amidesviavisible-light photoredox catalysis. The developed method shows excellent functional group tolerance with a broad substrate scope and good to excellent yields. Furthermore, control experiments and density functional theory (DFT) calculations are performed to gain insight into the reactivity and selectivity.
- Park, Jin,Park, Sehoon,Jang, Gwang Seok,Kim, Ran Hui,Jung, Jaehoon,Woo, Sang Kook
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supporting information
p. 9995 - 9998
(2021/10/06)
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- Organophotoredox-Mediated Amide Synthesis by Coupling Alcohol and Amine through Aerobic Oxidation of Alcohol
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The combination of an organic photocatalyst [4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6 dicyanobenzene) or 5MeOCzBN (2,3,4,5,6-pentakis(3,6-dimethoxy-9 H-carbazol-9-yl)benzonitrile)], quinuclidine, and tetra-n-butylammonium phosphate (hydrogen-bonding catalyst) was employed for amide bond formations. The hydrogen-bonded OH group activated the adjacent C?H bond of alcohols towards hydrogen atom transfer (HAT) by a radical species. The quinuclidinium radical cation, generated through single-electron oxidation of quinuclidine by the photocatalyst, employed to abstract a hydrogen atom from the α-C?H bond of alcohols selectively due to a polarity effect-produced α-hydroxyalkyl radical, which subsequently converted to the corresponding aldehyde under aerobic conditions. Then the coupling of the aldehyde and an amine formed a hemiaminal intermediate that upon photocatalytic oxidation produced the amide.
- Samanta, Samya,Shah, Sk. Sheriff,Shee, Maniklal,Singh, Amit Kumar,Singh, N. D. Pradeep,Venkatesh, Yarra
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- Ionic liquid catalyzed Ritter reaction/Pd-catalyzed directed Ortho-arylation; facile access to diverse libraries of biaryl-amides from Aryl-nitriles
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Diverse libraries of biaryl-amides bearing N-t-butyl and N-adamantyl groups were synthesized in two steps by the Ritter reaction of aryl-nitriles, using tBuOH and AdaOH as carbocation precursors, and employing [BMIM(SO3H)][OTf] (neat or with [B
- Sutar, Suraj M.,Savanur, Hemantkumar M.,Kalkhambkar, Rajesh G.,Borosky, Gabriela L.,Aridoss, Gopalakrishnan,Laali, Kenneth K.
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supporting information
(2020/10/30)
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- CoFe2O4?SiO2-NH-βCD-BF3 as a supramolecular nanocomposite: Synthesis, characterization and catalytic activity
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This manuscript describes synthesis of BF3-functionlized β-cylcodextrine grafted magnetic CoFe2O4 nanaoparticles as a hybrid magnetic nano-composite (CoFe2O4?SiO2-NH-βCD-BF3). The CoFe2O4?SiO2-NH-βCD-BF3 was fabricated by grafting of 6-O-toluenesulfonyl cyclodextrin (6-Ts-βCD) to 3-aminopropyl triethoxysilane coated magnetic CoFe2O4?SiO2 nanoparticles followed by combination with BF3. The CoFe2O4?SiO2-NH-βCD-BF3was characterized by FT-IR, TGA, VSM and SEM techniques. The feasibility of using CoFe2O4?SiO2-NH-βCD-BF3 as a magnetically recoverable catalyst was confirmed in the modified-Ritter reaction. The result showed that this novel nano-composite could serve as an efficient nanoreactor bearing super-acidic sites formed by immobilized BF3 and reuse at least for 6 times without loss in activity.
- Hamadi, Hosein,Zanjani, Zohreh,Yadollahi, Mahtab
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- Structure-Guided Modification of Heterocyclic Antagonists of the P2Y14 Receptor
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The P2Y14 receptor (P2Y14R) mediates inflammatory activity by activating neutrophil motility, but few classes of antagonists are known. We have explored the structure-activity relationship of a 3-(4-phenyl-1H-1,2,3-triazol-1-yl)-5-(aryl)benzoic acid antagonist scaffold, assisted by docking and molecular dynamics (MD) simulation at a P2Y14R homology model. A computational pipeline using the High Throughput MD Python environment guided the analogue design. Selection of candidates was based upon ligand-protein shape and complementarity and the persistence of ligand-protein interactions over time. Predictions of a favorable substitution of a 5-phenyl group with thiophene and an insertion of a three-methylene spacer between the 5-aromatic and alkyl amino moieties were largely consistent with empirical results. The substitution of a key carboxylate group on the core phenyl ring with tetrazole or truncation of the 5-aryl group reduced affinity. The most potent antagonists, using a fluorescent assay, were a primary 3-aminopropyl congener 20 (MRS4458) and phenyl p-carboxamide 30 (MRS4478).
- Yu, Jinha,Ciancetta, Antonella,Dudas, Steven,Duca, Sierra,Lottermoser, Justine,Jacobson, Kenneth A.
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supporting information
p. 4860 - 4882
(2018/06/20)
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- Oxidative C?H/C?H Cross-Coupling Reactions between N-Acylanilines and Benzamides Enabled by a Cp*-Free RhCl3/TFA Catalytic System
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By making use of a dual-chelation-assisted strategy, a completely regiocontrolled oxidative C?H/C?H cross-coupling reaction between an N-acylaniline and a benzamide has been accomplished for the first time. This process constitutes a step-economic and highly efficient pathway to 2-amino-2′-carboxybiaryl scaffolds from readily available substrates. A Cp*-free RhCl3/TFA catalytic system was developed to replace the [Cp*RhCl2]2/AgSbF6 system generally used in oxidative C?H/C?H cross-coupling reactions between two (hetero)arenes (Cp=pentamethylcyclopentadienyl, TFA=trifluoroacetic acid). The RhCl3/TFA system avoids the use of the expensive Cp* ligand and AgSbF6. As an illustrative example, the procedure developed herein greatly streamlines the total synthesis of the naturally occurring benzo[c]phenanthridine alkaloid oxynitidine, which was accomplished in excellent overall yield.
- Shi, Yang,Zhang, Luoqiang,Lan, Jingbo,Zhang, Min,Zhou, Fulin,Wei, Wenlong,You, Jingsong
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supporting information
p. 9108 - 9112
(2018/07/25)
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- A Visible-Light-Driven, Metal-free Route to Aromatic Amides via Radical Arylation of Isonitriles
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The photochemical metal-free carboamidation of aryl radicals has been exploited for the preparation of aromatic amides, including hetero- and polyaromatic derivatives, under visible light irradiation of arylazo sulfones in the presence of isocyanides in aqueous acetonitrile. The process was useful for the smooth preparation of the antidepressant moclobemide. (Figure presented.).
- Malacarne, Marco,Protti, Stefano,Fagnoni, Maurizio
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p. 3826 - 3830
(2017/11/15)
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- Atom economical synthesis of: N -alkylbenzamides via the iron(III) sulfate catalyzed rearrangement of 2-alkyl-3-aryloxaziridines in water and in the presence of a surfactant
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A green and mild synthetic route to N-alkylbenzamides involves eco-friendly one pot synthesis of 2-alkyl-3-aryloxaziridines from N-alkylamines and benzaldehydes followed by iron(iii) sulfate catalyzed rearrangement to the corresponding amides in water as the solvent and in the presence of sodium dodecyl sulfate as the surfactant. This green approach affords N-alkylbenzamides in high overall yields under simple and minimum manipulation.
- Kra?em, Jamil,Ollevier, Thierry
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p. 1263 - 1267
(2017/08/15)
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- Bu4NI-Catalyzed Oxygen-Centered Radical Addition between Acyl Peroxides and Isocyanides
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A novel oxygen-centered radical addition between acyl peroxides and isocyanides has been developed. A diverse collection of valuable arylcarboxyamides were easily synthesized by this protocol. From the preliminary mechanistic study, the elimination of carbon dioxide affords the product via an intramolecular rearrangement.
- Chen, Meng,Li, Yang,Tang, Hong,Ding, Hao,Wang, Kai,Yang, Lingen,Li, Cuiting,Gao, Meng,Lei, Aiwen
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supporting information
p. 3147 - 3150
(2017/06/23)
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- Cp?CoIII-Catalyzed syn-Selective C-H Hydroarylation of Alkynes Using Benzamides: An Approach Toward Highly Conjugated Organic Frameworks
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Hydroarylation of internal alkynes by cost-effective CoIII-catalysis, directed by N-tert-butyl amides, is achieved to avail mono- or dihydroarylated amide products selectively in an atom and step economic way. Several important functional groups were tolerated under the reaction conditions, and syn-hydroarylation products were exclusively isolated. Notably, a 4-fold C-H hydroarylation provided a highly conjugated organic framework in one step. Kinetic study with extensive deuterium labeling experiments were performed to support the proposed mechanism.
- Bera, Sourav Sekhar,Debbarma, Suvankar,Ghosh, Avick Kumar,Chand, Santanu,Maji, Modhu Sudan
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p. 420 - 430
(2017/04/26)
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- Organic template-free synthesis of zeolite Y nanoparticle assemblies and their application in the catalysis of the Ritter reaction
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Zeolite Y nanoparticle assemblies (Y-NA) with a mesoporous structure were directly synthesized at 75?°C for 16 h without adding any organic templates. The changes in structure, morphology and textural parameters of the materials obtained after different crystallization times were investigated via powder X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and N2-sorption. The results show that Y-NA had a micro-mesoporous structure composed of highly crystalline particle assemblies with sizes of 400-900 nm. The H-form Y-NA (HY-NA) is strongly acidic, and exhibits a good catalytic performance in the Ritter reaction, as compared with the H-form microporous zeolite Y and mesoporous zeolite ZSM-5.
- Tang, Ting,Zhang, Lei,Dong, Hai,Fang, Zhongxue,Fu, Wenqian,Yu, Quanyong,Tang, Tiandi
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p. 7711 - 7717
(2017/02/05)
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- Application of γ-Valerolactone as an Alternative Biomass-Based Medium for Aminocarbonylation Reactions
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γ-Valerolactone (GVL) was proposed as a renewable, nontoxic reaction medium with negligible vapor pressure for homogeneous Pd-catalyzed aminocarbonylation reactions. Iodobenzene as a model substrate and its 4-substituted derivatives were converted to the corresponding 2-ketocarboxamides with high conversions and chemoselectivities in γ-valerolactone. The effect of carbon monoxide pressure and reaction temperature on the conversion and selectivities were studied in the range 1–50 bar and 25–100 °C, respectively. The highest conversion and selectivity was achieved at 25 bar and 50 °C for iodobenzene in GVL for 24 h.
- Marosv?lgyi-Haskó, Diána,Lengyel, Blanka,Tukacs, József M.,Kollár, László,Mika, László T.
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p. 1224 - 1229
(2016/11/23)
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- Substituent effects in aminocarbonylation of para-substituted iodobenzenes
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Iodobenzene derivatives possessing various substituents (amino, hydroxy, tert-butyl, methyl, isopropyl, phenyl, fluoro, chloro, methoxycarbonyl, acetyl, trifluoromethyl, nitro) in the para position were aminocarbonylated using tert-butylamine and n-butylamine as N-nucleophiles. A palladium(0) catalyst formed in situ from palladium(II) acetate and triphenylphosphine was used. Carboxamide and ketocarboxamide type compounds were formed via single and double carbon monoxide insertion, respectively. While 4-substituents with negative Hammett constants (σp) decrease reactivity of the substrates, the iodoaromatics possessing electron-withdrawing group (characterized by positive Hammett constants (σp)) in the 4-position have shown high reactivity. Highly active catalysts were obtained in the presence of xantphos accompanied by the chemoselective formation of the corresponding carboxamides. The difference in reactivity of iodoarene and bromoarene functionalities enabled the synthesis of bromo-substituted compounds suitable for further functionalization.
- Marosv?lgyi-Haskó, Diána,Kégl, Tamás,Kollár, László
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supporting information
p. 7509 - 7516
(2016/11/11)
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- Exploiting the Reactivity of Isocyanide: Coupling Reaction between Isocyanide and Toluene Derivatives Using the Isocyano Group as an N1 Synthon
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An unusual oxidative coupling reaction of isocyanide and toluene derivatives using tetrabutylammonium iodide (TBAI) as a catalyst is disclosed. The experimental results and mechanistic study show that the isocyano group acts formally as an N1 synthon during the transformation, thus expanding the reactivity profile of isocyanide.
- Liu, Zhiqiang,Zhang, Xinglu,Li, Jian,Li, Jianxiong,Li, Feng,Li, Chunju,Jia, Xueshun
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p. 4052 - 4055
(2016/08/30)
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- TfOH catalyzed One-Pot Schmidt–Ritter reaction for the synthesis of amides through N-acylimides
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A One-Pot tandem Schmidt–Ritter process for the synthesis of amides has been developed using the super acid as catalyst. The in situ generated aryl/aliphatic nitriles from the reaction of aldehydes and sodium azide in the presence of TfOH and AcOH (Schmidt reaction) react with suitable alcohol (Ritter reaction) to give the amides. For the first time we observed that during the Schmidt process N-acylimides were generated along with nitriles, interestingly these N-acylimides also participated in the Ritter reaction.
- Singh, Garima,Dada, Ravikrishna,Yaragorla, Srinivasarao
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supporting information
p. 4424 - 4427
(2016/09/13)
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- Carboxylate-Assisted Iridium-Catalyzed C-H Amination of Arenes with Biologically Relevant Alkyl Azides
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An iridium-catalyzed C-H amination of arenes with a wide substrate scope is reported. Benzamides with electron-donating and -withdrawing groups and linear, branched, and cyclic alkyl azides are all applicable. Cesium carboxylate is crucial for both reactivity and regioselectivity of the reactions. Many biologically relevant molecules, such as amino acid, peptide, steroid, sugar, and thymidine derivatives can be introduced to arenes with high yields and 100 % chiral retention. Ir responsible! A direct C-H amination between benzamide derivatives and various alkyl azides was achieved using iridium catalysis (see scheme; NTf=trifluoromethanesulfonyl amide). Cesium carboxylate was found to be the promoter and regiocontroller of this reaction. By this method, many biological active molecules can be introduced to benzamide components with high yields and 100 % chiral retention.
- Zhang, Tao,Hu, Xuejiao,Wang, Zhen,Yang, Tiantian,Sun, Hao,Li, Guigen,Lu, Hongjian
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supporting information
p. 2920 - 2924
(2016/03/23)
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- Cesium Carboxylate-Promoted Iridium Catalyzed C-H Amidation/Cyclization with 2,2,2-Trichloroethoxycarbonyl Azide
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An Ir(III)-catalyzed direct C-H amidation/cyclization of benzamides using 2,2,2-trichloroethoxycarbonyl azide (TrocN3) as the aminocarbonyl source is reported. With the aid of cesium carboxylate, the reactions proceed efficiently and with high regioselectivity, producing various functionalized quinazoline-2,4(1H,3H)-diones, which are important building blocks and key synthetic intermediates for biologically and medicinally important compounds. During the reactions, two new C-N bonds were formed by breaking C-H and N-H bonds sequence.
- Zhang, Tao,Wang, Zhen,Hu, Xuejiao,Yu, Meng,Deng, Tianning,Li, Guigen,Lu, Hongjian
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p. 4898 - 4905
(2016/07/06)
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- One-pot sequential Schmidt and Ritter reactions for the synthesis of N-tert-butyl amides
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The first example of the direct conversion of benzaldehydes into their corresponding N-tert-butyl amides through a Schmidt reaction/Ritter reaction sequence is described. A reagent mixture consisting of NaN3 and HBF4?OEt2 in acetic acid efficiently reacts with aromatic and conjugated (α,β-unsaturated) aldehydes to produce nitrile derivatives, which in situ undergo a Ritter reaction with tert-butyl acetate to afford the corresponding N-tert-butyl amides in almost quantitative yields. The method needs no column chromatography purification. The wide substrate scope as well as the ready availability of the reagent system also make this protocol convenient.
- Hazarika, Nabajyoti,Baishya, Gakul
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supporting information
p. 5686 - 5690
(2014/10/15)
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- A transition-metal-free synthesis of arylcarboxyamides from aryl diazonium salts and isocyanides
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A transition-metal-free carboxyamidation process, using aryl diazonium tetrafluoroborates and isocyanides under mild conditions, has been developed. This novel conversion was initiated by a base and solvent induced aryl radical, followed by radical addition to isocyanide and single electron transfer (SET) oxidation, affording the corresponding arylcarboxyamide upon hydration of the nitrilium intermediate.
- Xia, Zhonghua,Zhu, Qiang
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p. 4110 - 4113
(2013/09/12)
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- Direct C-H amination of arenes with alkyl azides under rhodium catalysis
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New horizons in the utility of azides: The rhodium-catalyzed intermolecular direct C-H amination of arenes with alkyl azides provides a convenient route to N-alkyl anilines (see scheme; DG=directing group). Alkyl azides with a wide range of functional groups reacted readily with various substrates, including benzamides, aromatic ketones, and flavones. Copyright
- Shin, Kwangmin,Baek, Yunjung,Chang, Sukbok
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supporting information
p. 8031 - 8036
(2013/08/23)
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- Ir(III)-catalyzed mild C-H amidation of arenes and alkenes: An efficient usage of acyl azides as the nitrogen source
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Reported herein is the development of the Ir(III)-catalyzed direct C-H amidation of arenes and alkenes using acyl azides as the nitrogen source. This procedure utilizes an in situ generated cationic half-sandwich iridium complex as a catalyst. The reaction takes place under very mild conditions, and a broad range of sp2 C-H bonds of chelate group-containing arenes and olefins are smoothly amidated with acyl azides without the intervention of the Curtius rearrangement. Significantly, a wide range of reactants of aryl-, aliphatic-, and olefinic acyl azides were all efficiently amidated with high functional group tolerance. Using the developed approach, Z-enamides were readily accessed with a complete control of regio- and stereoselectivity. The developed direct amidation proceeds in the absence of external oxidants and releases molecular nitrogen as a single byproduct, thus offering an environmentally benign process with wide potential applications in organic synthesis and medicinal chemistry.
- Ryu, Jaeyune,Kwak, Jaesung,Shin, Kwangmin,Lee, Donggun,Chang, Sukbok
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supporting information
p. 12861 - 12868
(2013/09/23)
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- Rhodium-catalyzed direct C-H amination of benzamides with aryl azides: A synthetic route to diarylamines
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No muss, no fuss: A rhodium-catalyzed direct intermolecular C-H amination of benzamides and ketoximes using aryl azides as the amine source has been developed. The reaction exhibits a broad substrate scope with excellent functional-group tolerance, requires no external oxidants, releases N 2 as the only by-product, and produces diarylamines in high yields. Copyright
- Ryu, Jaeyune,Shin, Kwangmin,Park, Sae Hume,Kim, Ji Young,Chang, Sukbok
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supporting information
p. 9904 - 9908
(2012/10/29)
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- An efficient and scalable ritter reaction for the synthesis of tert-butyl amides
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A scalable procedure for the conversion of nitriles to N-tert-butyl amides via the Ritter reaction was optimized employing tert-butyl acetate and acetic acid. The reaction has a broad scope for aromatic, alkyl, and α,β-unsaturated nitriles.
- Baum, Jean C.,Milne, Jacqueline E.,Murry, Jerry A.,Thiel, Oliver R.
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supporting information; experimental part
p. 2207 - 2209
(2009/07/01)
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- FeCl3-catalyzed Ritter reaction. Synthesis of amides
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A safe and inexpensive synthesis of amides, from benzylic alcohols and nitriles and from t-butyl acetate and nitriles, using a Ritter reaction catalyzed by FeCl3·6H2O is described.
- Anxionnat, Bruno,Guérinot, Amandine,Reymond, Sébastien,Cossy, Janine
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experimental part
p. 3470 - 3473
(2009/09/28)
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- Practical synthesis of a p38 MAP kinase inhibitor
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p38 MAP kinase inhibitors have attracted considerable interest as potential agents for the treatment of inflammatory diseases. Herein, we describe a concise and efficient synthesis of inhibitor 1 that is based on a phthalazine scaffold. Highlights of our approach include a practical synthesis of a 1,6-disubstituted phthalazine building block 24 as well as the one-pot formation of boronic acid 27. Significant synthetic work to understand the reactivity principles of the intermediates helped in selection of the final synthetic route. Subsequent optimization of the individual steps of the final sequence led to a practical synthesisof 1.
- Achmatowicz, Michal,Thiel, Oliver R.,Wheeler, Philip,Bernard, Charles,Huang, Jinkun,Larsen, Robert D.,Faul, Margaret M.
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scheme or table
p. 795 - 809
(2009/06/20)
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- Amide derivative
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A compound of the formula: wherein Ar is optionally substituted phenyl, etc.; n is 0, 1 or 2; R1is hydogen atom, optionally substituted alkyl, etc.; R2and R3are independently optionally substituted alkyl, etc.; R4and R5are independently hydrogen atom or optionally substituted alkyl; R6is hydrogen atom, hydroxy or alkyl; or a pharmaceutically acceptable salt thereof is useful as a medicament for treating retinal degenerative disorders and the like.
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- Insecticidal N-heterocyclylalkyl-or N-[(polycyclyl)alkyl]-N′substituted piperazines
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Compounds of the following structure are disclosed as effective insecticides: in which: A and B are independently lower alkyl; U is lower alkylidene, lower alkenylidene, or CH—Z, where Z is hydrogen, lower alkyl, lower cycloalkyl, or phenyl; R is phenyl o
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- New nonsteroidal steroid 5α-reductase inhibitors. Syntheses and structure-activity studies on carboxamide phenylalkyl-substituted pyridones and piperidones
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In the search for nonsteroidal inhibitors of 5α-reductase for the treatment of benign prostatic hyperplasia (BPH), we synthesized diisopropyl (1a-8a) and tert-butyl (1b-8b) benzamides, as well as ethyl benzoates (1c, 3c), which were substituted in 4 posit
- Hartmann, Rolf W.,Reichert, Martin
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p. 145 - 153
(2007/10/03)
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- Benzamide-containing pharmaceutical compositions
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A group of benzamide compounds are disclosed that are formed into pharmaceutical compositions for oral or intravenous administration to patients suffering from neurodegenerative conditions associated with dopamine depletion.
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