- 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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- 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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- 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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- 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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- 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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- Aza-DielsAlder reaction between N-aryl-1-oxo-1H-isoindolium ions and tert-enamides: Steric effects on reaction outcome
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The synthesis of 5-substituted 6,6a-dihydroisoindolo[2,1-a]quinolin-11(5H)- ones via [4 + 2] imino-DielsAlder cyclization from N-aryl-3- hydroxyisoindolinones and N-vinyl lactams under Lewis acid-catalysed anhydrous conditions is reported. Reactions of N-(2-substituted-aryl)-3- hydroxyisoindolinones with N-vinylpyrrolidone under identical conditions resulted in the formation of 2-(2-substitued-aryl)-3-(2-(2-oxopyrrolidin-1-yl) vinyl)isoindolin-1-one analogues indicating steric hinderance as the cause of deviation. The probable mechanism of the reaction based on the results from X-ray crystallography and molecular modelling is discussed.
- Jha, Amitabh,Chou, Ting-Yi,ALJaroudi, Zainab,Ellis, Bobby D.,Cameron, T. Stanley
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supporting information
p. 848 - 857
(2014/05/06)
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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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- 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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- 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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- Intermolecular oxidative C-N bond formation under metal-free conditions: Control of chemoselectivity between aryl sp2 and benzylic sp 3 C-H bond imidation
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A new synthetic approach toward intermolecular oxidative C-N bond formation of arenes has been developed under transition-metal-free conditions. Complete control of chemoselectivity between aryl sp2 and benzylic sp 3 C-H bond imidation was achieved by the choice of nitrogen sources, representatively being phthalimide and dibenzenesulfonimide, respectively.
- Kim, Hyun Jin,Kim, Jiyu,Cho, Seung Hwan,Chang, Sukbok
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supporting information; experimental part
p. 16382 - 16385
(2011/12/13)
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- A convenient procedure for the synthesis of phthalimides under microwave irradiation
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An efficient, extremely fast and clean procedure for the synthesis of phthalimides 2 and 3 by the reaction of phthalic anhydrides 1 with urea and aromatic amines in the presence of catalytic amount of DMF under microwave irradiation is described. The products are obtained in quantitative yields and excellent purities.
- Mogilaiah,Reddy, G. Randheer
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p. 882 - 884
(2007/10/03)
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- Thalidomide analogues demonstrate dual inhibition of both angiogenesis and prostate cancer
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The identification of agents with antiproliferative activity against endothelial cells has significant value for the treatment of many angiogenesis-dependent pathologies. Herein, we describe the discovery of a series of thalidomide analogues possessing inhibitory effects against both endothelial and prostate cancer cells. More specifically, several analogues exhibited low micromolar to mid-nanomolar potency in the inhibition of human microvascular endothelial cell (HMEC) proliferation, both in the presence and absence of vascular endothelial growth factor (VEGF), with the tetrafluorophthalimido class of compounds demonstrating the greatest potency. Additionally, all the compounds were screened against two different androgen independent prostate cancer cell lines (PC-3 and DU-145). Again, the tetrafluorophthalimido analogues exhibited the greatest effect with GI 50 values in the low micromolar range. Thalidomide was found to demonstrate selective inhibition of androgen receptor positive LNCaP prostate cancer cells. Furthermore, we showed that, as an example, tetrafluorophthalimido analogue 19 was able to completely inhibit the prostate specific antigen (PSA) secretion by the LNCaP cell line, while thalidomide demonstrated a 70% inhibition. We have also demonstrated that a correlation exists between HMEC and prostate cancer cell proliferation for this structural class. Altogether, our study suggests that these analogues may serve as promising leads for the development of agents that target both androgen dependent and independent prostate cancer and blood vessel growth.
- Capitosti, Scott M.,Hansen, Todd P.,Brown, Milton L.
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p. 327 - 336
(2007/10/03)
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- New reaction of ethenetetracarbonitrile with N-arylisoindolines
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N-Arylisoindolines 1a-i react with ethenetetracarbonitrile 2 in aerated benzene by formation of [3-(2-aryl-3-dicyanomethylene-2,3-dihydro-1H-isoindol-1-ylidene)-2-aryl-2, 3-dihydro-1H-isoindol-1-ylidene]propanedinitriles 8a-i (20-36%), N-aryl-3-dicyanomethylene-isoindol-2-ones 9a-i (15-21%) and N-arylphthalimides 10a-i (4-9%) as well as 1,1,2,2-tetracyanoethane 11 (35-55%). The structure of 8d has been unambiguously confirmed by a single crystal X-ray structure analysis. A rationale for the formation of products 8-11 is presented.
- D?pp, Dietrich,Hassan, Alaa A.,Mourad, Aboul-Fetouh E.,Nour El-Din, Ahmed M.,Angermund, Klaus,Krüger, Carl,Lehmann, Christian W.,Rust, J?rg
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p. 5073 - 5081
(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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- Protection of amino group as N-phthalyl derivative using microwave irradiation
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The amino groups for various substrates are protected as N-phthalyl derivatives using solvent free neat condition under microwave exposure.
- Khadilkar, Bhushan M.,Madyar, Virendra R.
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p. 1083 - 1085
(2007/10/03)
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- Process for the production of cyclic carboxylic acid imides
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In a process for reacting an aromatic or hydroaromatic alicyclic or heterocyclic dicarboxylic acid or its anhydride with an aliphatic or aromatic alicyclic or heterocyclic mono- or di-amine to produce an N-substituted dicarboxylic acid imide with a splitting off of water, the improvement of carrying out the reaction in a liquid solvent mixture consisting essentially of a non-polar organic solvent and a strongly polar organic solvent which together form a ternary azeotrope with water at reaction temperatures between about 40°C. and 160°C. The imide products are generally known for use as intermediates and final products in a number of industries.
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