- Palladium-Catalyzed Chlorocarbonylation of Aryl (Pseudo)Halides Through In Situ Generation of Carbon Monoxide
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An efficient palladium-catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high-value products from readily available aryl (pseudo)halides. The combination of palladium(0), Xantphos, and an amine base is essential to promote this broadly applicable catalytic reaction. Overall, this reaction provides access to a great variety of carbonyl-containing products through in situ transformation of the generated aroyl chloride. Combined experimental and computational studies support a reaction mechanism involving in situ generation of CO.
- Bismuto, Alessandro,Boehm, Philip,Morandi, Bill,Roediger, Sven
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supporting information
p. 17887 - 17896
(2020/08/19)
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- Ru-Catalyzed Selective C-H Bond Hydroxylation of Cyclic Imides
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We report on cyclic imides as weak directing groups for selective monohydroxylation reactions using ruthenium catalysis. Whereas acyclic amides are known to promote the hydroxylation of the C(sp2)-H bond enabling five-membered ring ruthenacycle intermediates, the cyclic imides studied herein enabled the hydroxylation of the C(sp2)-H bond via larger six-membered ruthenacycle intermediates. Furthermore, monohydroxylated products were exclusively obtained (even in the presence of overstoichiometric amounts of reagents), which was rationalized by the difficulty to accommodate coplanar intermediates once the first hydroxyl group was introduced into the substrate. The same reactivity was observed in the presence of palladium catalysts.
- Yuan, Yu-Chao,Bruneau, Christian,Dorcet, Vincent,Roisnel, Thierry,Gramage-Doria, Rafael
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p. 1898 - 1907
(2019/02/05)
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- Br?nsted acid mediated intramolecular cyclopropane ring expansion/[4 + 2]-cycloaddition
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A cascade reaction of 3-hydroxy-2-phenylisoindolin-1-one and cyclopropyl ketone has been developed via a Br?nsted acid-promoted ring-opening/intramolecular cross-cycloaddition/[4 + 2]-cycloaddition process. The developed methodology provides straightforward access to pentacyclic isoindolin-1-one derivatives under simple reaction conditions.
- Li, Jian,Zhu, Shangrong,Xu, Qiuneng,Liu, Li,Yan, Shenghu
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p. 10004 - 10008
(2019/12/23)
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- Palladium-Catalyzed β-Arylation of Amide via Primary sp3C-H Activation
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A β-arylation of primary sp3C-H bonds on simple amides such as pivalamides with aryl iodides/CF3CO2Ag has been established successfully at 120 °C in a Pd(OAc)2 (catalyst)/CF3CH2OH (solvent) system. Pivalamides including tBuCONH2, tBuCONHR, and tBuCONR2 undergo the arylations smoothly to afford β-aryl pivalamides in moderate to good yields. Various aryl iodides are available bearing either electron-donating or electron-withdrawing substituted groups in the coupling reactions.
- Zhao, Ren,Lu, Wenjun
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supporting information
p. 2188 - 2192
(2018/07/25)
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- Direct Pd(II)-Catalyzed Site-Selective C5-Arylation of 2-Pyridone Using Aryl Iodides
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A straightforward Pd(II)-catalyzed general strategy was developed for the C5-selective arylation of the 2-pyridone core with easily available aryl iodides. The transformation was highly regioselective and accomplished with a wide scope and functional group tolerance. Silver nitrate played a crucial role in this direct site-selective arylation. The method was extended to synthesize biologically active molecules.
- Maity, Saurabh,Das, Debapratim,Sarkar, Souradip,Samanta, Rajarshi
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supporting information
p. 5167 - 5171
(2018/09/13)
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- Phthalimide-N-sulfonic acid, an efficient catalyst for the synthesis of various isoindoline-1,3-dione derivatives
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An environmentally friendly method is described for the synthesis of various isoindoline-1,3-dione derivatives from the reaction of phthalic anhydride with aromatic/aliphatic amines in ethanol at 80 °C by phthalimide-N-sulfonic acid as an efficient heterogeneous acid catalyst. Some advantages include the metal-free and environmentally friendly protocol, simple operation and reusable processes, easy recovery, short reaction times, and high yields.
- Habibi, Davood,Pordanjani, Hossein Mohammadkhani
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p. 2293 - 2299
(2017/10/05)
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- Unmasking Amides: Ruthenium-Catalyzed Protodecarbonylation of N-Substituted Phthalimide Derivatives
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The unprecedented transformation of a wide range of synthetically appealing phthalimides into amides in a single-step operation has been achieved in high yields and short reaction times using a ruthenium catalyst. Mechanistic studies revealed a unique, homogeneous pathway involving five-membered ring opening and CO2 release with water being the source of protons.
- Yuan, Yu-Chao,Kamaraj, Raghu,Bruneau, Christian,Labasque, Thierry,Roisnel, Thierry,Gramage-Doria, Rafael
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supporting information
p. 6404 - 6407
(2017/12/08)
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- Thermolysis and radiofluorination of diaryliodonium salts derived from anilines
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Aniline-derived diaryliodonium salts were synthesized and functionalized in good to excellent yields by judicious utilization of electron-withdrawing protecting groups. This simple approach opens another route to radiolabeling amino arenes in relatively complex molecules, such as flutemetamol.
- Linstad, Ethan J.,Vāvere, Amy L.,Hu, Bao,Kempinger, Jayson J.,Snyder, Scott E.,DiMagno, Stephen G.
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supporting information
p. 2246 - 2252
(2017/03/17)
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- Synthetic method for N-substituted imide
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The invention provides a synthetic method for N-substituted imide. According to the method, aromatic ketone and amine are used as substrates, air or oxygen is used as an oxygen source, and cyclic imide is produced under liquid phase conditions under the action of a catalyst. The method is mild in conditions, high in oxidation efficiency and high in product yield; and since the method uses air or oxygen as the oxygen source, the method is economic and environment-friendly and has good application prospect.
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Paragraph 0016; 0028; 0029; 0030; 0031
(2017/04/20)
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- Cuprous Oxide Catalyzed Oxidative C-C Bond Cleavage for C-N Bond Formation: Synthesis of Cyclic Imides from Ketones and Amines
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Selective oxidative cleavage of a C-C bond offers a straightforward method to functionalize organic skeletons. Reported herein is the oxidative C-C bond cleavage of ketone for C-N bond formation over a cuprous oxide catalyst with molecular oxygen as the oxidant. A wide range of ketones and amines are converted into cyclic imides with moderate to excellent yields. In-depth studies show that both α-C-H and β-C-H bonds adjacent to the carbonyl groups are indispensable for the C-C bond cleavage. DFT calculations indicate the reaction is initiated with the oxidation of the α-C-H bond. Amines lower the activation energy of the C-C bond cleavage, and thus promote the reaction. New insight into the C-C bond cleavage mechanism is presented.
- Wang, Min,Lu, Jianmin,Ma, Jiping,Zhang, Zhe,Wang, Feng
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supporting information
p. 14061 - 14065
(2016/01/25)
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- Regioselective gold-catalyzed oxidative C-N bond formation
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A novel protocol for the regioselective intermolecular amination of various arenes has been developed. By using an I(III) oxidant in the presence of a Au(I) catalyst, a direct and novel route for regioselectively accessing a variety of substituted aniline moieties has been achieved with yields as high as 90%. Mechanistic insight suggests that regioselectivity can be predicted based on electrophilic aromatic metalation patterns.
- Marchetti, Louis,Kantak, Abhishek,Davis, Riley,Deboef, Brenton
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supporting information
p. 358 - 361
(2015/01/30)
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- Transition metal free intramolecular selective oxidative C(sp3)-N coupling: Synthesis of N-aryl-isoindolinones from 2-alkylbenzamides
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A synthetic method has been developed for the preparation of biologically important isoindolinones including indoprofen and DWP205190 drugs from 2-alkylbenzamide substrates by transition metal-free intramolecular selective oxidative coupling of C(sp3)-H and N-H bonds utilizing iodine, potassium carbonate and di-tert-butyl peroxide in acetonitrile at 110-140 °C.
- Verma, Ajay,Patel, Saket,Meenakshi,Kumar, Amit,Yadav, Abhimanyu,Kumar, Shailesh,Jana, Sadhan,Sharma, Shubham,Prasad, Ch. Durga,Kumar, Sangit
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supporting information
p. 1371 - 1374
(2015/02/18)
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- A phthalimidation protocol that follows protein defined parameters
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This work outlines the first phthalimidation protocol suitable for protein labeling and performed in aqueous media at room temperature and neutral pH with no catalyst or co-reagent required. The methodology is suitable for a range of amines and its efficiency was determined with chemoselective and site-selective protein labeling. This journal is
- Singudas, Rohith,Adusumalli, Srinivasa Rao,Joshi, Pralhad Namdev,Rai, Vishal
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supporting information
p. 473 - 476
(2015/01/09)
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- Catalyst-free, eco-friendly, one-pot syntheses of 2-(3H-imidazo [4,5-b] pyridine-2-yl)-N-arylbenzamides in water
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Eco-friendly, one-pot three-component syntheses of 2-(3H-imidazo [4,5-b]pyridine-2-yl)-N-arylbenzamides have been developed by combining phthalic anhydride with anilines and pyridine-2,3-diamine in water without any catalyst. These reactions involves easy workup, provide good yields and use of water as solvent which were the merits of this preparation.
- Reddy, Y. Dathu,Kumar, P. Praveen,Devi, B. Rama,Reddy, Ch. Venkata Ramana,Dubey
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p. 768 - 773
(2015/04/14)
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- Synthesis and TNF expression inhibitory properties of new thalidomide analogues derived via Heck cross coupling
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A library of new thalidomide analogues containing an olefin functionality were synthesised using a Heck cross coupling reaction from their aryl halogenated precursor. All analogues were tested for their ability to inhibit the synthesis of the proinflammatory cytokine Tumour Necrosis Factor (TNF). Compounds 22, 29, 33 and 37 were the most effective in this assay inhibiting TNF expression 50%, 69%, 52% and 50%, respectively. Crown Copyright
- Stewart, Scott G.,Spagnolo, Daniel,Polomska, Marta E.,Sin, Melvin,Karimi, Mahdad,Abraham, Lawrence J.
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p. 5819 - 5824
(2008/03/13)
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- Comparison of copper(II) acetate promoted N-arylation of 5,5-dimethyl hydantoin and other imides with triarylbismuthanes and aryl boronic acids
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This work demonstrates that the copper acetate promoted N-arylation of imides with boronic acids can be employed as a major method for the synthesis of N3-aryl hydantoins. Georg Thieme Verlag Stuttgart.
- Hügel, Helmut M.,Rix, Colin J.,Fleck, Karin
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p. 2290 - 2292
(2007/10/03)
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