- A convenient synthesis of N-tert-butyl amides by the reaction of di-tert-butyl dicarbonate and nitriles catalyzed by Cu(OTf)2
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The utility of Cu(OTf)2 as the catalyst for the synthesis of a series of N-tert-butyl amides in excellent isolated yields via the reaction of nitriles (alkyl, aryl, benzyl, and furyl nitriles) with di-tert-butyl dicarbonate is described. Cu(OTf)2 is a highly stable and efficient catalyst for the present Ritter reaction under solvent-free conditions at room temperature.
- Chen, Junqing,Feng, Chengliang,Ji, Min,Tang, Yuqi,Yang, Wanfeng
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p. 602 - 608
(2020/04/27)
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- Amide Synthesis by Nickel/Photoredox-Catalyzed Direct Carbamoylation of (Hetero)Aryl Bromides
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Herein, we report a one-electron strategy for catalytic amide synthesis that enables the direct carbamoylation of (hetero)aryl bromides. This radical cross-coupling approach, which is based on the combination of nickel and photoredox catalysis, proceeds at ambient temperature and uses readily available dihydropyridines as precursors of carbamoyl radicals. The method's mild reaction conditions make it tolerant of sensitive-functional-group-containing substrates and allow the installation of an amide scaffold within biologically relevant heterocycles. In addition, we installed amide functionalities bearing electron-poor and sterically hindered amine moieties, which would be difficult to prepare with classical dehydrative condensation methods.
- Alandini, Nurtalya,Buzzetti, Luca,Candish, Lisa,Collins, Karl D.,Favi, Gianfranco,Melchiorre, Paolo,Schulte, Tim
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supporting information
p. 5248 - 5253
(2020/03/03)
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- Nickel-catalyzed aminocarbonylation of Aryl/Alkenyl/Allyl (pseudo)halides with isocyanides and H2O
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Herein described is a nickel-catalyzed aminocarbonylation of aryl/alkenyl/allyl (pseudo)halides with isocyanides, providing aryl/alkenyl/allyl amides in 41% to 92% yields. Functional groups such as F, Cl, OMe, and heteroaromatic rings are compatible in the reaction. A Ni(0)/Ni(II) catalytic cycle is proposed based on preliminary experiments and previous literature. The reaction features readily available nickel salt, broad functional group tolerance, and simple reaction conditions.
- Li, Qiao,Cai, Yun,Jin, Hongwei,Liu, Yunkui,Zhou, Bingwei
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supporting information
(2020/11/27)
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- An efficient synthesis of N-tert-butyl amides by the reaction of tert-butyl benzoate with nitriles catalyzed by Zn(ClO4)2·6H2O
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An efficient, mild and inexpensive synthesis of N-tert-butyl amides from the reaction of nitriles (aryl, benzyl and sec-alkyl nitriles) with tert-butyl benzoate catalyzed by the employment of 2?mol% Zn(ClO4)2·6H2O at 50?°C
- Feng, Cheng-Liang,Yan, Bin,Zhang, Min,Chen, Jun-Qing,Ji, Min
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p. 535 - 542
(2019/02/12)
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- Transamidation of: N -acyl-glutarimides with amines
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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
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p. 1322 - 1329
(2018/03/06)
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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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- 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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- Efficient Approach to Amide Bond Formation with Nitriles and Peroxides: One-Pot Access to Boronated β-Ketoamides
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An efficient, mild and practical approach for the synthesis of amides from nitriles and peroxides is reported in the presence of boron trifluoride ethereate. In this protocol, we utilized peroxides as C1 synthons for the amidation reaction. Als
- Gore, Babasaheb Sopan,Senadi, Gopal Chandru,Garkhedkar, Amol Milind,Wang, Jeh-Jeng
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supporting information
p. 3014 - 3021
(2017/09/08)
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- Palladium/Copper-Catalyzed Oxidative Coupling of Arylboronic Acids with Isocyanides: Selective Routes to Amides and Diaryl Ketones
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An efficient and alternative oxidative cross-coupling strategy starting from arylboronic acids and isocyanides for the selective synthesis of amides and diaryl ketones with palladium/copper catalysis is developed. Various substituted benzamides and benzop
- Lu, Fangling,Chen, Ziyue,Li, Zhen,Wang, Xiaoyan,Peng, Xinyue,Li, Cong,Fang, Lingtong,Liu, Dong,Gao, Meng,Lei, Aiwen
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supporting information
p. 3954 - 3957
(2017/08/14)
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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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- 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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p. 7509 - 7516
(2016/11/11)
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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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- 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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- Complete Switch of Selectivity in the C-H Alkenylation and Hydroarylation Catalyzed by Iridium: The Role of Directing Groups
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A complete switch in the CpIr(III)-catalyzed paths between C-H olefination and hydroarylation was found to be crucially dependent on the type of directing groups. This dichotomy in product distribution was correlated to the efficiency in attaining syn-coplanarity of olefin-inserted 7-membered iridacycles. Theoretical studies support our hypothesis that the degree of flexibility of this key intermediate modulates the β-H elimination, which ultimately affords the observed chemoselectivity.
- Kim, Jiyu,Park, Sung-Woo,Baik, Mu-Hyun,Chang, Sukbok
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supporting information
p. 13448 - 13451
(2015/11/09)
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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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- Synthesis of phosphoramidates: A facile approach based on the C-N bond formation via Ir-catalyzed direct C-H amidation
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A new synthetic route to phosphoramidates by intermolecular C-H amidation is presented. Substrates with assorted directing groups were activated by an iridium-based catalyst system and reacted with a number of phosphoryl azides, executing efficient phosphoramidate synthesis via C-N bond formations. (Chemical Equation Presented).
- Kim, Hyunwoo,Park, Juhyeon,Kim, Jeung Gon,Chang, Sukbok
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supporting information
p. 5466 - 5469
(2015/01/09)
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- Ruthenium-catalyzed direct C-H amidation of arenes including weakly coordinating aromatic ketones
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C-H activation: The ruthenium-catalyzed direct sp2 C-H amidation of arenes by using sulfonyl azides as the amino source is presented (see scheme). A wide range of substrates were readily amidated including arenes bearing weakly coordinating groups. Synthetic utility of the thus obtained products was demonstrated in the preparation of biologically active heterocycles. Copyright
- Kim, Jiyu,Kim, Jinwoo,Chang, Sukbok
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supporting information
p. 7328 - 7333
(2013/06/27)
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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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- KAl(SO4)2.12H2O as an eco-friendly and reusable catalyst for the synthesis of amides by the Ritter reaction
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KAl(SO4)2.12H2O (Alum) is an eco-friendly, inexpensive, readily available and reusable and was applied as catalyst to the synthesis of N-alkyl amides from nitriles and alcohols by the Ritter reaction. This solvent-free procedure is very simple with excellent yields and easy work-up.
- Sadeghi, Bahareh,Farahzadi, Ebrahim,Hassanabadi, Alireza
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p. 539 - 540
(2012/10/30)
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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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- Synthesis of amides via palladium-catalyzed amidation of aryl halides
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A new and efficient method for the synthesis of amides via palladium-catalyzed C-C coupling of aryl halides with isocyanides is reported, by which a series of amides were formed from readily available starting materials under mild conditions. This transformation could extend its use to the synthesis of natural products and significant pharmaceuticals.(Figure Presented)
- Jiang, Huanfeng,Liu, Bifu,Li, Yibiao,Wang, Azhong,Huang, Huawen
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supporting information; experimental part
p. 1028 - 1031
(2011/04/27)
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- One-pot synthesis of N-tert-butyl amides from alcohols, ethers and esters using ZnCl2/SiO2 as a recyclable heterogeneous catalyst
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ZnCl2/SiO2 has been found to be an efficient and reusable catalyst for conversion of alcohols, ethers and esters to corresponding amides via the Ritter reaction in high yield. It was found that benzonitrile reacted with tert-butyl acetate faster than the other sources of tert-butyl carbocation.
- Tamaddon, Fatemeh,Tavakoli, Fatemeh
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experimental part
p. 52 - 55
(2011/04/24)
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- Iodine-catalyzed one-pot synthesis of amides from nitriles via Ritter reaction
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Ritter reactions of alcohols and tert-butyl acetate with various nitriles were performed using iodine as a mild and effective catalyst under heating conditions to afford the corresponding amides in good to excellent yields.
- Theerthagiri, Palani,Lalitha, Appaswami,Arunachalam, Pirama Nayagam
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supporting information; experimental part
p. 2813 - 2819
(2010/07/04)
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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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- Synthesis of amides using the Ritter reaction with bismuth triflate catalysis
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N-tert-Alkyl and aryl amides were obtained by a Ritter reaction of various nitriles with tertiary alcohols in the presence of a catalytic amount of bismuth triflate.
- Callens, Emmanuel,Burton, Andrew J.,Barrett, Anthony G.M.
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p. 8699 - 8701
(2007/10/03)
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- Increasing rates and scope of reactions: Sluggish amines in microwave-heated aminocarbonylation reactions under air
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Commercially available molybdenum hexacarbonyl serves as a convenient and solid carbon monoxide source in palladium-catalyzed aminocarbonylations of aryl bromides and iodides. This improved microwave protocol, relying on DBU as base and THF as solvent, enables rapid couplings using otherwise sluggish anilines, tert-butylamine, and free amino acids. In addition, Cr(CO)6 and W(CO)6 were found to be useful alternative CO-releasing reagents. Altogether, 16 different aromatic amides were synthesized under air in 35-95% yield after only 15 min of controlled microwave irradiation.
- Wannberg, Johan,Larhed, Mats
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p. 5750 - 5753
(2007/10/03)
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- Amide therapeutics for the treatment of inflammatory bowel disease
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Disclosed are methods for treating or preventing inflammatory bowel disease (IBD) using amide and related compounds. Pharmaceutical compositions containing amide compounds which are useful for the treatment or prophylaxis of IBD are also disclosed.
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- Autoxidation Reactions of Imines to form Oxaziridines and Amides
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The formation of oxaziridines and the isomeric amides in equal amounts by the spontaneous autoxidation of several liquid imines via peroxyimidic acid intermediates is reported.
- Auret, Barbara J.,Boyd, Derek R.,Coulter, Peter B.
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p. 463 - 464
(2007/10/02)
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