- Equivalent Loading of Directed Arenes in Pd(II)-Catalyzed Oxidative Cross-Coupling of Aryl C-H Bonds at Room Temperature
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The unsymmetrical biaryls (Ar1-Ar2) produced by the catalytic cross-couplings of aryl halides (Ar1-halo) with aryl metallics (Ar2-M) in the loading ratio of 1:1 are popular in chemical synthesis. In contrast, there has been less precedence on the same biaryls produced effectively from two normal aryl C-H bonds with equivalent loading. Here, we report that, in a palladium/oxidant/acid catalytic system at room temperature, one arene (Ar1-H, 1 equiv) can highly selectively couple with the other one (Ar2-H, 1 equiv) to afford the target Ar1-Ar2 just by controlling the directing groups and the substituted groups on their phenyl rings. The utility of this one-one cross-coupling is also demonstrated by synthesis of a few bioactive molecules.
- Mei, Chong,Zhao, Mengdi,Lu, Wenjun
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p. 2714 - 2733
(2021/02/01)
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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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- PPh3/I2/HCOOH: An efficient CO source for the synthesis of phthalimides
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A straightforward and general method has been developed for the synthesis of phthalimide derivatives from 2-iodobenzamides and PPh3/I2/HCOOH in the presence of a catalytic amount of Pd(OAc)2. The reaction results demonstrate that PPh3/I2/HCOOH is a facile, efficient and safe CO source. The whole process is carried out in toluene at 80 °C and furnishes the desired products in good to excellent yields.
- Wang, Yingying,Zhou, Yang,Lei, Min,Hou, Jinjun,Jin, Qinghao,Guo, Dean,Wu, Wanying
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p. 1180 - 1185
(2019/01/26)
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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.
- -
-
Paragraph 0016; 0028; 0029; 0030; 0031
(2017/04/20)
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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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- A facile and practical copper diacetate mediated, ligand free C-N cross coupling of trivalent organobismuth compounds with amines and N-heteroarenes
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In present work, an efficient Cu(OAc)2·H2O catalyzed protocol in the absence of any additional ligand has been developed for the N-arylation of amines and nitrogen containing heterocycles using trivalent organobismuth reagents under mild conditions. This protocol tolerates a variety of functional groups on amines and the organobismuth reagent with a high degree of chemoselectivity.
- Jadhav,Pardeshi
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p. 14531 - 14537
(2016/02/19)
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- H-β-zeolite catalyzed transamidation of carboxamides, phthalimide, formamides and thioamides with amines under neat conditions
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Efficient transamidation of unactivated carboxamides, phthalimides, formamides and thioamides with amines under solvent-free conditions using H-β-zeolite as a green and recyclable heterogeneous catalyst is described. Easy work up, high purity of the products, recyclability and environmentally-friendly nature of the catalyst are the attractive features of the present methodology. This is the first report for the transamidation of thioamides under heterogeneous conditions.
- Rao, Sadu Nageswara,Chandra Mohan, Darapaneni,Adimurthy, Subbarayappa
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p. 95313 - 95317
(2015/11/24)
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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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- N -aminopyridinium salts as precursors for N-centered radicals - Direct amidation of arenes and heteroarenes
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Readily prepared N-aminopyridinium salts are valuable precursors for the generation of N-centered radicals. Reduction of these salts by single electron transfer allows for clean generation of amidyl radicals. It is shown that direct radical C-H amination of heteroarenes and arenes can be achieved with N-aminopyridinium salts under mild conditions by using photoredox catalysis.
- Greulich, Tobias W.,Daniliuc, Constantin G.,Studer, Armido
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supporting information
p. 254 - 257
(2015/03/05)
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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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- 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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- N-acyloxyphthalimides as nitrogen radical precursors in the visible light photocatalyzed room temperature C-H amination of arenes and heteroarenes
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This paper reports a room temperature visible light photocatalyzed method for the C-H amination of arenes and heteroarenes. A key enabling advance in this work is the design of N-acyloxyphthalimides as precursors to nitrogen-based radical intermediates for these transformations. A broad substrate scope is presented, including the selective meta-amination of pyridine derivatives. A radical aromatic substitution mechanism is proposed.
- Allen, Laura J.,Cabrera, Pablo J.,Lee, Melissa,Sanford, Melanie S.
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supporting information
p. 5607 - 5610
(2014/05/06)
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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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- Metal-free intermolecular oxidative C-N bond formation via tandem C-H and N-H bond functionalization
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The development of a novel intermolecular oxidative amination reaction, a synthetic transformation that involves the simultaneous functionalization of both a N-H and C-H bond, is described. The process, which is mediated by an I(III) oxidant and contains no metal catalysts, provides a rapid and green method for synthesizing protected anilines from simple arenes and phthalimide. Mechanistic investigations indicate that the reaction proceeds via nucleophilic attack of the phthalimide on an aromatic radical cation, as opposed to the electrophilic aromatic amination that has been reported for other I(III) amination reactions. The application of this new reaction to the synthesis of a variety of substituted aniline derivatives is demonstrated.
- Kantak, Abhishek A.,Potavathri, Shathaverdhan,Barham, Rose A.,Romano, Kaitlyn M.,Deboef, Brenton
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supporting information; experimental part
p. 19960 - 19965
(2012/01/13)
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- Photoinduced electron transfer cyclizations of aryl-linked phthalimides
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The photochemistry of arene-linked phthalimides incorporating the carboxylate or thioether donor group was investigated. Simple N-phthalimidophenyl alkanoates exclusively gave photoreduction (CO 2H/H-exchange) products. In contrast, ω-phthalimido-meta- phenoxy carboxylates underwent photodecarboxylative cyclizations in yields of 6-48%. Likewise, catechol-linked derivatives furnished analogue cyclization products in 18-38% yield. Using the photodecarboxylation protocol, macrocyclic target compounds with ring sizes up to 17 could thus be realized. Two model phthalimides containing a thioether branch at the ortho-position of the arene-linker gave the analogue seven-membered cyclization products in yields of 28% and 35%, respectively.
- Lee, Yong-Jun,Ahn, Do-Hwan,Lee, Kyoung-Sub,Kim, Ae Rhan,Yoo, Dong Jin,Oelgem?ller, Michael
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experimental part
p. 5029 - 5031
(2011/10/09)
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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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- A simple copper salt catalyzed N-arylation of amines, amides, imides, and sulfonamides with arylboronic acids
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A simple copper salt catalyzed N-arylation reaction with arylboronic acids is reported. In the presence of a catalytic amount of a simple copper salt, the coupling of arylboronic acids with imides was performed in MeOH to give N-arylimides in excellent yields; a variety of amines, amides and sulfonamides could also be successfully coupled with arylboronic acids to give corresponding N-arylated products in moderate yields.
- Lan, Jing-Bo,Zhang, Guo-Lin,Yu, Xiao-Qi,You, Jing-Song,Chen, Li,Yan, Mei,Xie, Ru-Gang
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p. 1095 - 1097
(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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- N-phenylphthalimide-type cyclooxygenase (COX) inhibitors derived from thalidomide: Substituent effects on subtype selectivity
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Several N-substituted phenylphthalimide and phenylhomophthalimide derivatives with cyclooxygenase (COX)-inhibitory activity were prepared during structural development studies based on thalidomide as a lead compound. Substituent effects on the subtype selectivity were investigated.
- Sano, Hiroko,Noguchi, Tomomi,Tanatani, Aya,Miyachi, Hiroyuki,Hashimoto, Yuichi
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p. 1021 - 1022
(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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- 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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