- Electroselective and Controlled Reduction of Cyclic Imides to Hydroxylactams and Lactams
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An efficient and practical electrochemical method for selective reduction of cyclic imides has been developed using a simple undivided cell with carbon electrodes at room temperature. The reaction provides a useful strategy for the rapid synthesis of hydroxylactams and lactams in a controllable manner, which is tuned by electric current and reaction time, and exhibits broad substrate scope and high functional group tolerance even to reduction-sensitive moieties. Initial mechanistic studies suggest that the approach heavily relies on the utilization of amines (e.g., i-Pr2NH), which are able to generate α-aminoalkyl radicals. This protocol provides an efficient route for the cleavage of C-O bonds under mild conditions with high chemoselectivity.
- Bai, Ya,Shi, Lingling,Zheng, Lianyou,Ning, Shulin,Che, Xin,Zhang, Zhuoqi,Xiang, Jinbao
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supporting information
p. 2298 - 2302
(2021/04/05)
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- Visible-Light-Induced Metal-/Photocatalyst-Free C-H Bond Imidation of Arenes
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In this study, a visible-light-induced intermolecular C-H bond imidation of arenes was achieved at ambient condition. By using simple phthalimide with (diacetoxyiodo)benzene and molecular iodine, direct metal-/photocatalyst-free C-N bond formation was achieved. The imidation protocol was designed by using time-dependent density functional theory calculations and experimentally demonstrated for 28 substrates with as high as 96% yield. Mechanistic studies indicated that radical-mediated aromatic substitution occurred via photolysis of N-iodophthalimide under visible-light irradiation.
- Kuribara, Takahito,Nakajima, Masaya,Nemoto, Tetsuhiro
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supporting information
p. 2235 - 2239
(2020/03/13)
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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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- Method for one-step constructing N-(4-fluorophenyl) phthalimide by utilizing imine as initial raw material
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The invention discloses a method for one-step constructing N-(4-fluorophenyl) phthalimide by utilizing imine as an initial raw material. According to the method, (E)-N-(4-fluorophenyl)-1-phenyl methylenimine is taken as a reaction raw material and is subj
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Paragraph 0022-0024; 0035-0038; 0041-0046; 0051-0054
(2019/02/04)
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- Carbonylation Access to Phthalimides Using Self-Sufficient Directing Group and Nucleophile
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Herein we report a novel palladium-catalyzed oxidative carbonylation reaction for the synthesis of phthalimides with high atom- and step-economy. In our strategy, the imine and H2O, which are generated in situ from the condensation of aldehyde and amine, serve as self-sufficient directing group and nucleophile, respectively. This method provides rapid access to phthalimides starting from readily available materials in a one-pot manner. Various phthalimide derivatives are constructed efficiently, including medicinally and biologically active phthalimide-containing compounds.
- Ji, Fanghua,Li, Jianxiao,Li, Xianwei,Guo, Wei,Wu, Wanqing,Jiang, Huanfeng
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p. 104 - 112
(2018/02/19)
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- An efficient synthesis of N-substituted phthalimides using SiO2-tpy-Nb as heterogeneous and reusable catalyst
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A novel and efficient heterogeneous catalyst SiO2-tpy-Nb was developed, and its application in the preparation of N-substituted phthalimides from o-phthalic acids or anhydrides with amines provides the desired products in good to excellent yields. The catalyst was stable and recoverable for eight consecutive cycles without a significant loss in its activity. Furthermore, the catalyst is applicable in continuous flow which indicates its potential utilization in industrialization.
- Wan, Li,Sun, Xiaoning,Shi, Songjie,Zhang, Jiawei,Li, Xin,Li, Zhenjiang,Guo, Kai
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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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- Palladium-Catalyzed Synthesis of 1H-Indenes and Phthalimides via Isocyanide Insertion
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A new and versatile multicomponent domino strategy has been developed for the synthesis of a series of 1H-indene and phthalimide derivatives from simple and readily available starting materials. This process operating under mild conditions shows a broad substrate scope with moderate to excellent yields.
- Wang, Xu,Xiong, Wenfang,Huang, Yubing,Zhu, Jiayi,Hu, Qiong,Wu, Wanqing,Jiang, Huanfeng
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p. 5818 - 5821
(2017/11/10)
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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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- Facile synthesis of 3-substituted isoindolinones Dedicated to the memory of Professor Sharon Roscoe, a colleague and mentor instrumental in shaping the careers of many chemists
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The reactions of N-aryl-3-hydroxyisoindolinones and alkyl aryl ketones under Lewis acid-catalyzed anhydrous conditions afforded the corresponding substituted isoindolinones in good to excellent yields.
- Al-Jaroudi, Zainab,Mohapatra, Prabhu P.,Jha, Amitabh
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supporting information
p. 772 - 777
(2016/02/05)
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- Copper-Mediated Functionalization of Aryl Trifluoroborates
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This paper describes the Cu(OTf)2-mediated coupling of aryl and heteroaryl trifluoroborates with tetrabutylammonium or alkali metal salts to form C-O, C-N, and C-halogen bonds. The reactions proceed under mild conditions (often room temperature over 16 hours) with carboxylate, halide, and azide salts, all nucleophiles that have been underrepresented in the copper cross-coupling literature. Preliminary results show that copper salts bearing weakly coordinating X-type ligands are essential for enabling these transformations to proceed under mild conditions.
- Schimler, Sydonie D.,Sanford, Melanie S.
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supporting information
p. 2279 - 2284
(2016/10/06)
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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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- 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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- Efficient conversion of acids and esters to amides and transamidation of primary amides using OSU-6
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OSU-6, an MCM-41 type hexagonal mesoporous silica with strong Bronsted acid properties, has been used to promote the high-yield conversion of carboxylic acids and esters to carboxamides as well as transamidations of primary amides in a one-pot solventless approach. A metal-free heterogeneous catalyst that promotes all of these processes has not been previously reported. OSU-6 enables these transformations to proceed in shorter times and at lower temperatures for a broad range of substrates. An added benefit is that the catalyst can be recycled and reused multiple times without significant loss of activity.
- Nammalwar, Baskar,Muddala, Nagendra Prasad,Watts, Field M.,Bunce, Richard A.
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p. 9101 - 9111
(2015/11/09)
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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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- Magnetic nanocatalyst for the synthesis of maleimide and phthalimide derivatives
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An efficient and green protocol for the synthesis of N-aryl maleimide and phthalimide derivatives has been developed. The high efficiency of the catalyst was observed due to the homogeneous distribution of the nanoparticles. The catalyst was fully characterised by physicochemical methods such as IR spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction, dynamic light scattering (DLS), energy dispersive X-ray spectrum and zeta potential measurement techniques. The ease of separation of the catalyst from the reaction mixture and its high activity are eco-friendly attributes of this system.
- Thale, Pranila B.,Borase, Pravin N.,Shankarling, Ganapati S.
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p. 59454 - 59461
(2015/02/19)
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- Synthesis and antiseizure evaluation of isoindoline-1,3-dione derivatives in mice
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Epilepsy is the most common serious chronic noninfective neurological condition in the world. Despite the presence of various antiepileptic drugs in the market for epileptic patients, the necessity for development and discovery of novel antiepileptic drugs is felt. In fact, only 60-70 % of patients respond to the current drugs, and a high incidence of adverse effects is also observed. In the present study, a new series of phthalimide derivatives (compounds 3a-3m) were synthesized through the reaction of phthalic anhydride and various derivatives of aniline in toluene solvent (Reflux, 24 h). Antiepileptic activity of synthesized compounds (3a-3m) was investigated using two experimental models namely, maximal electroshock (MES) and pentylenetetrazole (PTZ), and the obtained results were compared with diazepam as reference drug. Neurotoxicity of compounds was also evaluated using rotarod model. Compound 3m with para methoxy substituent exhibited the anticonvulsant activity at 15.1 ± 1.53 (12.23-17.96) mg/kg dose in MES model compared to other derivatives. Unfortunately, none of the tested compounds rendered acceptable protection in subcutaneous PTZ model.
- Aliabadi, Alireza,Gholamine, Babak,Karimi, Tahereh
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p. 2736 - 2743
(2014/05/06)
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- Nitrogen-centered radical-mediated C-H imidation of arenes and heteroarenes via visible light induced photocatalysis
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The C-H imidation of arenes and heteroarenes has been achieved via visible light induced photocatalysis. In the presence of an iridium(iii) photoredox catalyst, the reaction of aromatic substrates with N-chlorophthalimide furnishes the N-aryl products at room temperature through a nitrogen-centered radical mediated aromatic substitution.
- Kim, Hyejin,Kim, Taehoon,Lee, Dong Gil,Roh, Sang Weon,Lee, Chulbom
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supporting information
p. 9273 - 9276
(2014/08/05)
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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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- Chitosan: An efficient recyclable catalyst for transamidation of carboxamides with amines under neat conditions
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A novel chitosan-catalyzed transamidation of carboxamides with amines under solvent-free conditions is described. A series of amide derivatives as well as more challenging aryl and alkyl amines with long-chain alkyl substituents could be selectively converted into the corresponding transamidation products, which are frequently found in biologically active compounds and pharmaceuticals. Under similar reaction conditions benzo[d]heterocycles were also obtained via a one-pot synthesis through transamidation and subsequent dehydration. Recyclability of chitosan was demonstrated, with quantitative yields of products obtained without any loss of catalytic activity. the Partner Organisations 2014.
- Nageswara Rao, Sadu,Chandra Mohan, Darapaneni,Adimurthy, Subbarayappa
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supporting information
p. 4122 - 4126
(2014/10/15)
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- Sterically controlled, palladium-catalyzed intermolecular amination of arenes
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We report the Pd-catalyzed amination of arenes to form N-aryl phthalimides with regioselectivity controlled predominantly by steric effects. Mono-, di-, and trisubstituted arenes lacking a directing group undergo amination reactions with moderate to high yields and high regioselectivities from sequential addition of PhI(OAc)2 as an oxidant in the presence of Pd(OAc) 2 as catalyst. This sterically derived selectivity contrasts that for analogous arene acetoxylation.
- Shrestha, Ruja,Mukherjee, Paramita,Tan, Yichen,Litman, Zachary C.,Hartwig, John F.
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supporting information
p. 8480 - 8483
(2013/07/19)
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- Imidazole-promoted synthesis of n-substituted phthalimide from N,N'-disubstituted ureas in solventless conditions
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A series of N-substituted phthalimides was synthesized by a thermal reaction between N,N0-disubstituted ureas and phthalic acid catalyzed by imidazole in solventless conditions. The products have been obtained in moderate to good yields (53-92%). Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications1 to view the free supplemental file. Copyright Taylor & Francis Group, LLC.
- Neves Filho, Ricardo A. W.,Palm-Forster, Mieder A. T.,De Oliveira, Ronaldo N.
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supporting information
p. 1571 - 1576
(2013/05/22)
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- Crystal structures and triboluminescence based on trifluoromethyl and pentafluorosulfanyl substituted asymmetric N-phenyl imide compounds
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A series of asymmetric N-phenyl imides with trifluoromethyl and pentafluorosulfanyl substituents at the terminal phenyl position have been prepared. They are colorless both in solution and the solid state, and they show blue emission in the solid state. X-ray crystal structure analysis of trifluoromethyl and pentafluorosulfanyl substituted derivatives revealed highly ordered noncentrosymmetric molecular arrangements with large net-dipole moments related to the piezoelectric behavior. XRD measurements of the powders afforded intense sharp reflection peaks, indicating formation of the lamellar ordering. By grinding with a spatula, their solids showed vivid blue triboluminescence.
- Nakayama, Hikaru,Nishida, Jun-Ichi,Takada, Noriyuki,Sato, Hiroyasu,Yamashita, Yoshiro
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experimental part
p. 671 - 676
(2012/06/15)
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- Palladium-catalyzed one-step synthesis of isoindole-1,3-diones by carbonylative cyclization of o-halobenzoates and primary amines
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(Chemical Equation Presented) The palladium-catalyzed aminocarbonylation of o-halobenzoates produces 2-substituted isoindole-1,3-diones in good yields. This methodology provides a good one-step approach to this important class of heterocycles and tolerates a variety of functional groups, including methoxy, alcohol, ketone, and nitro groups.
- Worlikar, Shilpa A.,Larock, Richard C.
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supporting information; experimental part
p. 7175 - 7180
(2009/05/09)
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- Synthesis and screening of anilides having olefinic and alkyl moiety in the side chain as chemical hybridizing agents for wheat (Triticum aestivum L.)
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Induction of male sterility by deployment of chemical hybridizing agents (CHAs) holds immense potential in heterosis breeding of wheat. A total of 21 anilides having different aromatic substitutions and side-chain variation were synthesized and screened as CHAs on three genotypes of wheat viz., PBW 343, HW 2046, and HD 2733, at winter season. Various anilides having vinyl moiety in the acyl side chain were synthesized by condensation between substituted anilines with different esters or acid chlorides. Another lead in the form of N-alkyl anilines also became evident. The percent male sterility data caused by CHAs revealed the significant contribution of anilides containing vinyl double bond incorporated in the form of closed ring structure viz., furyl moiety as the side chain. 4′-Fluoro-furyl anilide (1) and 4′-bromo-furyl anilide (2) are found to be promising lead CHAs for the design of highly active molecules. QSAR analysis revealed a direct relationship of field effect exemplified by the Swain-Lupton constant Fp for the aromatic substitution but an inverse relationship of molar refractivity MR for the side chain. The negative influences of parachor for the acyl domain have been underlined. The real guiding principle for selectivity of CHA action was found to be the π value. The CHAs act by mimicking UDP-glucose, the key substrate in the synthesis of callose, or lead to an imbalance in acid-base equilibrium in pollen mother cells resulting in dissolution of callose wall by premature callase secretion.
- Chakraborty, Kajal,Devakumar
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p. 5959 - 5968
(2007/10/03)
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- Synthesis and hypolipidemic activity of N-substituted phthalimides. Part V
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A series of N-aryl- or N-(1,2,4-triazol-yl)-phthalimides (4a-4i) have been synthesized starting from phthalic anhydride (1) and an appropriate amine (2a-2i). All compounds presented hypolipidemic activity, but compound 4d proved to be the most active and reduced plasma cholesterol and triglyceride levels in Swiss white mice significantly.
- Sena, Vera L.M.,Srivastava, Rajendra M.,Silva, Ricardo O.,Lima, Vera L.M.
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p. 1283 - 1288
(2007/10/03)
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- Microwave-assisted parallel synthesis of a 2-aryl-1H-isoindole-1,3-dione library
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An efficient parallel synthesis of a representative 28-member library of phthalimides is described. Parallel chromatography afforded the library members in suitable purity and with high yields.
- Barchín, Bernardo M.,Cuadro, Ana M.,Alvarez-Builla, Julio
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p. 343 - 345
(2007/10/03)
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- Multivariate regression with substituent shift increments. IV. 2-(4-X-phenyl)-1,3-dihydro-2H-isoindole-1,3-diones and 3-(4-X-phenyl)-3,4-dihydro-2H-1,3-benzoxazine-2,4-diones
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Two series of para disubstituted benzenes were studied: 2-(4-X-phenyl)-1,3-dihydro-2H-isoindole-1,3-diones (1) and 3-(4-X-phenyl)-3,4-dihydro-2H-1,3-benzoxazine-2,4-diones (2). Their 1H and 13C chemical shifts were correlated with substituent shift increments (SSI) aj and zj, respectively. For 13C chemical shifts, all four zj values, zj, zo, zm, and zp, were used to check the assignment and to find out possible variables for improvement of regression equations. Significant deviations from plain additivity were observed in the case of δH3 and δC3 chemical shifts. This can be explained by changes in diamagnetic anisotropy contribution induced by different twist of 4-substituent from the benzene plane caused by variable substituent in position 1.
- Holik, Miroslav,Friedl, Zdenek,Waisser, Karel,Gregor, Jiri
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p. 1709 - 1726
(2007/10/03)
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- Ullmann condensation using copper or copper oxide as the reactant. Arylation of active hydrogen compounds (imides, amides, amines, phenol, benzoic acid, and phenylacetylene)
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Ullmann condensation using Cu or copper oxide as the reactant and using no base has been studied.Reactions of active N-H, O-H, and C-H compounds, RZH (imides, amides, amines, phenol, benzoic acid, and phenylacetylene), with mixtures of aryl halides and more than a stoichiometric amount of Cu or copper oxide (Cu2O or CuO) without addition of base lead to facile arylation of the active hydrogen compounds.In the arylation reaction Cu and copper oxides serve not only as the catalyst but also as the acceptor of halogen from aryl halide.The reactivity of phenyl halide, PhX, increases in the order PhCli, the temperature where the phenylation starts, and the pKa value of the active hydrogen compound has been observed.A mechanism involving initial formation of an RZ-Cu species by the reaction between RZH and Cu or copper oxide and ensuing attack of organic halide at the RZ-Cu species is proposed.
- Yamamoto, Takakazu,Kurata, Yasundo
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- HYDROLYSIS OF 1-OXO-3-ETHYL-4-ARYL-2,3-BEZOXAZINIUM SALTS
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Irrespective of the character of the substituent at position 4, the action of triethyloxonium fluoroborate on 1-oxo-4-aryl(methyl)-2,3-benzoxazines leads to the formation of 1-oxo-3-ethyl-4-aryl(methyl)-2,3-benzoxazinium tetrafluoroborates, which readily exchange the anion, being converted into the corresponding perchlorates and tetrachloroferrates.Hydrolysis of the oxobenzoxazinium perchlorates leads to 4-hydroxy-3-ethyl-4-aryl(methyl)-2,3-benzoxazin-1-ones, which exhibit the characteristics of carbinol bases.The formation of N-arylphthalimides is also observed in the case of the oxobenzoxazinium salts containing accepting or weakly don ating substituents.
- Volynets, N. F.,Samartseva, I. V.,Pavlova, L. A.
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p. 574 - 577
(2007/10/02)
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