- Metal-free transamidation of benzoylpyrrolidin-2-one and amines under aqueous conditions
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N-Acyl lactam amides, such as benzoylpyrrolidin-2-one, benzoylpiperidin-2-one, and benzoylazepan-2-one reacted with amines in the presence of DTBP and TBAI to afford the transamidated products in good yields. The reactions were conducted under aqueous conditions and good functional group tolerance was achieved. Both aliphatic and aromatic primary amines displayed good activity under metal-free conditions. A radical reaction pathway is proposed.
- Joseph, Devaneyan,Lee, Sunwoo,Park, Myeong Seong
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supporting information
p. 6227 - 6232
(2021/07/28)
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- A practical and sustainable protocol for direct amidation of unactivated esters under transition-metal-free and solvent-free conditions
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In this paper, a NaOtBu-mediated synthesis approach was developed for direct amidation of unactivated esters with amines under transition-metal-free and solvent-free conditions, affording a series of amides in good to excellent yields at room temperature. In particular, an environmentally friendly and practical workup procedure, which circumvents the use of organic solvents and chromatography in most cases, was disclosed. Moreover, the gram-scale production of representative products3a,3wand3auwas efficiently realized by applying operationally simple, sustainable and practical procedures. Furthermore, this approach was also applicable to the synthesis of valuable molecules such as moclobemide (a powerful antidepressant), benodanil and fenfuram (two commercial agricultural fungicides). These results demonstrate that this protocol has the potential to streamline amide synthesis in industry. Meanwhile, quantitative green metrics of all the target products were evaluated, implying that the present protocol is advantageous over the reported ones in terms of environmental friendliness and sustainability. Finally, additional experiments and computational calculations were carried out to elucidate the mechanistic insight of this transformation, and one plausible mechanism was provided on the basis of these results and the related literature reports.
- Chen, Cheng,Cheng, Hua,Du, Min-Chen,Qian, Liang,Qin, Xin,Sang, Wei,Yao, Wei-Zhong,Yuan, Ye,Zhang, Rui
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supporting information
p. 3972 - 3982
(2021/06/17)
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- Manganese Catalyzed Direct Amidation of Esters with Amines
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The transition metal catalyzed amide bond forming reaction of esters with amines has been developed as an advanced approach for overcoming the shortcomings of traditional methods. The broad scope of substrates in transition metal catalyzed amidations remains a challenge. Here, a manganese(I)-catalyzed method for the direct synthesis of amides from a various number of esters and amines is reported with unprecedented substrate scope using a low catalyst loading. A wide range of aromatic, aliphatic, and heterocyclic esters, even in fatty acid esters, reacted with a diverse range of primary aryl amines, primary alkyl amines, and secondary alkyl amines to form amides. It is noteworthy that this approach provides the first example of the transition metal catalyzed amide bond forming reaction from fatty acid esters and amines. The acid-base mechanism for the manganese(I)-catalyzed direct amidation of esters with amines was elucidated by DFT calculations.
- Fu, Zhengqiang,Wang, Xinghua,Tao, Sheng,Bu, Qingqing,Wei, Donghui,Liu, Ning
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p. 2339 - 2358
(2021/02/03)
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- Electrochemical Synthesis of Carbazoles by Dehydrogenative Coupling Reaction
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A constant current protocol, employing undivided cells, a remarkably low supporting electrolyte concentration, inexpensive electrode materials, and a straightforward precursor synthesis enabling a novel access to N-protected carbazoles by anodic N,C bond formation using directly generated amidyl radicals is reported. Scalability of the reaction is demonstrated and an easy deblocking of the benzoyl protecting group is presented.
- Kehl, Anton,Schupp, Niclas,Breising, Valentina M.,Schollmeyer, Dieter,Waldvogel, Siegfried R.
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supporting information
p. 15847 - 15851
(2020/11/02)
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- Highly Chemoselective, Transition-Metal-Free Transamidation of Unactivated Amides and Direct Amidation of Alkyl Esters by N-C/O-C Cleavage
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The amide bond is one of the most fundamental functional groups in chemistry and biology and plays a central role in numerous processes harnessed to streamline the synthesis of key pharmaceutical and industrial molecules. Although the synthesis of amides is one of the most frequently performed reactions by academic and industrial scientists, the direct transamidation of tertiary amides is challenging due to unfavorable kinetic and thermodynamic contributions of the process. Herein, we report the first general, mild, and highly chemoselective method for transamidation of unactivated tertiary amides by a direct acyl N-C bond cleavage with non-nucleophilic amines. This operationally simple method is performed in the absence of transition metals and operates under unusually mild reaction conditions. In this context, we further describe the direct amidation of abundant alkyl esters to afford amide bonds with exquisite selectivity by acyl C-O bond cleavage. The utility of this process is showcased by a broad scope of the method, including various sensitive functional groups, late-stage modification, and the synthesis of drug molecules (>80 examples). Remarkable selectivity toward different functional groups and within different amide and ester electrophiles that is not feasible using existing methods was observed. Extensive experimental and computational studies were conducted to provide insight into the mechanism and the origins of high selectivity. We further present a series of guidelines to predict the reactivity of amides and esters in the synthesis of valuable amide bonds by this user-friendly process. In light of the importance of the amide bond in organic synthesis and major practical advantages of this method, the study opens up new opportunities in the synthesis of pivotal amide bonds in a broad range of chemical contexts.
- Li, Guangchen,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
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supporting information
p. 11161 - 11172
(2019/08/07)
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- Nickel-Catalyzed Amide Bond Formation from Methyl Esters
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Despite being one of the most important and frequently run chemical reactions, the synthesis of amide bonds is accomplished primarily by wasteful methods that proceed by stoichiometric activation of one of the starting materials. We report a nickel-catalyzed procedure that can enable diverse amides to be synthesized from abundant methyl ester starting materials, producing only volatile alcohol as a stoichiometric waste product. In contrast to acid- and base-mediated amidations, the reaction is proposed to proceed by a neutral cross coupling-type mechanism, opening up new opportunities for direct, efficient, chemoselective synthesis.
- Ben Halima, Taoufik,Masson-Makdissi, Jeanne,Newman, Stephen G.
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supporting information
p. 12925 - 12929
(2018/09/14)
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- Well-Defined, Air-Stable, and Readily Available Precatalysts for Suzuki and Buchwald-Hartwig Cross-coupling (Transamidation) of Amides and Esters by N-C/O-C Activation
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A general class of well-defined, air-stable, and readily available Pd(II)-NHC precatalysts (NHC = N-heterocyclic carbene) for Suzuki and Buchwald-Hartwig cross-coupling of amides (transamidation) and esters by selective N-C/O-C cleavage is reported. Since these precatalysts are highly active and the easiest to synthesize, the study clearly suggests that [Pd(NHC)(acac)Cl] should be routinely included during the development of new cross-coupling methods. An assay for in situ screening of NHC salts in this cross-coupling manifold is presented.
- Zhou, Tongliang,Li, Guangchen,Nolan, Steven P.,Szostak, Michal
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supporting information
p. 3304 - 3309
(2019/05/10)
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- Pd-PEPPSI: A general Pd-NHC precatalyst for Buchwald-Hartwig cross-coupling of esters and amides (transamidation) under the same reaction conditions
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Amides are of fundamental interest in many fields of chemistry involving organic synthesis, chemical biology and biochemistry. Here, we report the first catalytic Buchwald-Hartwig coupling of both common esters and amides by highly selective C(acyl)-X (X = O, N) cleavage to rapidly access aryl amide functionality via a cross-coupling strategy. Reactions are promoted by versatile, easily prepared, well-defined Pd-PEPPSI type precatalysts, and proceed in good to excellent yields and with excellent chemoselectivity for the acyl bond cleavage. The method is user friendly because it employs commercially-available, moisture- and air-stable precatalysts. Notably, for the first time we demonstrate selective C(acyl)-N and C(acyl)-O cleavage/Buchwald-Hartwig amination under the same reaction conditions, which allows for streamlining amide synthesis by avoiding restriction to a particular acyl metal precursor. Of broad interest, this study opens the door to using a family of well-defined Pd(ii)-NHC precatalysts bearing pyridine "throw-away" ligands for the selective C(acyl)-amination of bench-stable carboxylic acid derivatives.
- Shi, Shicheng,Szostak, Michal
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supporting information
p. 10584 - 10587
(2017/09/29)
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- A Cross-Coupling Approach to Amide Bond Formation from Esters
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A palladium-catalyzed cross-coupling between aryl esters and anilines is reported, enabling access to diverse amides. The reaction takes place via activation of the C-O bond by oxidative addition with a Pd-NHC complex, which enables the use of relatively non-nucleophilic anilines that otherwise require stoichiometric activation with strong bases in order to react. High yields of aromatic, aliphatic, and heterocyclic products are obtained. A range of activated esters are evaluated in the presence and absence of catalyst, demonstrating that the catalytic methodology substantially increases the types of electrophiles that can be utilized for amide bond formation in the absence of harsh bases.
- Ben Halima, Taoufik,Vandavasi, Jaya Kishore,Shkoor, Mohanad,Newman, Stephen G.
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p. 2176 - 2180
(2017/08/09)
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- Palladium-catalyzed regio- and chemoselective direct desulfitative arylation of anilides with arylsulfonyl chlorides
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A straightforward and practical palladium-catalyzed regioselective arylation of anilides is described. This method provides a new approach to prepare 2-aminobiaryls, which are valuable precursors for the synthesis of various N-containing heterocycles, using arylsulfonyl chlorides as readily available arylating agents.
- Kianmehr, Ebrahim,Tanbakouchian, Arezoo
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p. 5337 - 5343
(2017/08/11)
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- A General Method for Two-Step Transamidation of Secondary Amides Using Commercially Available, Air- and Moisture-Stable Palladium/NHC (N-Heterocyclic Carbene) Complexes
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The first general method is reported for transamidation of secondary carboxamides catalyzed by Pd-NHC (NHC = N-heterocyclic carbene) complexes. Commercially available, air- and moisture-stable (NHC)Pd(R-allyl)Cl complexes can effect C-N cross-coupling of a wide range of N-Boc and N-Ts amides, obtained by selective amide N-functionalization, with non-nucleophilic anilines and sterically hindered amines in very good yields. The first use of versatile Pd-NHC complexes as catalysts is represented for transition-metal-catalyzed C(acyl)-N amination of amides by N-C activation.
- Meng, Guangrong,Lei, Peng,Szostak, Michal
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supporting information
p. 2158 - 2161
(2017/04/27)
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- Visible-Light-Promoted C-H Arylation by Merging Palladium Catalysis with Organic Photoredox Catalysis
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The use of a dual palladium/organic photoredox catalytic system enables the directed arylation of arenes with aryldiazonium salts with a broad substrate scope at room temperature under mild reaction conditions. This study thus serves as not only an alternative route for the biaryl motifs but also a new example for the application of an organic photoredox catalyst.
- Jiang, Jian,Zhang, Wen-Man,Dai, Jian-Jun,Xu, Jun,Xu, Hua-Jian
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p. 3622 - 3630
(2017/04/11)
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- Novel compound or pharmaceutically acceptable salt thereof and pharmaceutical composition for prevention or treatment of disease caused by influenza virus infection containing the same as an active ingredient
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The present invention relates to a novel compound or a pharmaceutically acceptable salt thereof, and a pharmaceutical composition comprising the same as an active component for preventing or treating diseases related with influenza virus infection. The novel compound represented by chemical formula 1 has remarkable antivirus activity against influenza virus without cytotoxicity to human cells and thus has little side effects to human bodies. Therefore, the pharmaceutical composition having the same as an active component can be usefully used for preventing or treating diseases which occur through influenza virus infection such as flu, cold, sore throat, bronchitis, pneumonia, avian influenza, swine flu, goat flu, etc.COPYRIGHT KIPO 2016
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Paragraph 0867; 0869; 0870
(2016/10/07)
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- NEW IRIDIUM-BASED COMPLEXES FOR ECL
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The present invention relates to novel iridium-based Ir(III) luminescent complexes, conjugates comprising these complexes as a label and their application, e.g. in the electrochemiluminescence based detection of an analyte.
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- NEW IRIDIUM-BASED COMPLEXES FOR ECL
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The present invention relates to novel iridium-based Ir(III) luminescent complexes, conjugates comprising these complexes as a label and their application, e.g. in the electrochemiluminescence based detection of an analyte.
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- NEW IRIDIUM-BASED COMPLEXES FOR ECL
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The present invention relates to novel iridium-based Ir(III) luminescent complexes, conjugates comprising these complexes as a label and their application, e.g. in the electrochemiluminescence based detection of an analyte.
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- NEW BIS-IRIDIUM-COMPLEXES FOR MANUFACTURING OF ECL-LABELS
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The present invention relates to novel bis-iridium-based Ir(III) complexes, labels manufactured using these complexes and a method for producing such complexes.
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- Novel compound or pharmaceutically acceptable salt thereof and pharmaceutical composition for prevention or treatment of disease caused by influenza virus infection containing the same as an active ingredient
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The present invention relates to a novel compound or a pharmaceutically acceptable salt thereof, and a pharmaceutical composition for preventing or treating diseases caused by influenza virus infection, comprising the same as an active ingredient. The nov
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Paragraph 0867; 0869; 0870
(2016/10/07)
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- Novel compound or pharmaceutically acceptable salt thereof and pharmaceutical composition for prevention or treatment of disease caused by influenza virus infection containing the same as an active ingredient
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The present invention relates to a novel compound or pharmaceutically acceptable salt thereof, and to a pharmaceutical composition containing the same as an active ingredient for treating and preventing disease caused by influenza virus infection. The novel compound represented by chemical formula 1 according to the present invention not only has extremely excellent antivirus activity, but also has less side effects for a human body by not having cytotoxicity for a human cell. Therefore, a pharmaceutical composition containing the same as an active ingredient can be used in preventing or treating such as flu, colds, sore throats, bronchitis, pneumonia, bird flu, swine flu, and goat flu caused by influenza virus infection.COPYRIGHT KIPO 2015
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Paragraph 0867; 0869; 0870
(2016/10/08)
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- A highly efficient Pd-catalyzed decarboxylative ortho-arylation of amides with aryl acylperoxides
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An efficient Pd-catalyzed decarboxylative ortho-arylation of amides with aryl acylperoxides was developed. A variety of anilides reacted with aryl acylperoxides to afford the corresponding ortho-arylation products, and N-methoxyarylamides generated phenanthridinones. This journal is
- Li, Dengke,Xu, Ning,Zhang, Yicheng,Wang, Lei
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p. 14862 - 14865
(2014/12/11)
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- NEW IRIDIUM-BASED COMPLEXES FOR ECL
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The present invention relates to novel iridium-based Ir(III) luminescent complexes, conjugates comprising these complexes as a label and their application, e.g. in the electrochemiluminescence based detection of an analyte.
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Page/Page column 41
(2014/02/16)
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- NEW BIS-IRIDIUM-COMPLEXES FOR MANUFACTURING OF ECL-LABELS
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The present invention relates to novel bis-iridium-based Ir(III) complexes, labels manufactured using these complexes and a method for producing such complexes.
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Page/Page column 23; 24
(2014/02/16)
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- NEW IRIDIUM-BASED COMPLEXES FOR ECL
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The present invention relates to novel iridium-based Ir(III) luminescent complexes, conjugates comprising these complexes as a label and their application, e.g. in the electrochemiluminescence based detection of an analyte.
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Page/Page column 36; 37
(2014/02/16)
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- NEW IRIDIUM-BASED COMPLEXES FOR ECL
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Novel iridium-based Ir(III) luminescent complexes, conjugates comprising these complexes as a label and their application, for example in the electrochemiluminescence based detection of an analyte.
- -
-
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- NEW IRIDIUM-BASED COMPLEXES FOR ECL
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The present invention relates to novel iridium-based Ir(III) luminescent complexes, conjugates comprising these complexes as a label and their application, e.g. in the electrochemiluminescence based detection of an analyte.
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-
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- NEW IRIDIUM-BASED COMPLEXES FOR ECL
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The present invention relates to novel iridium-based Ir(III) luminescent complexes, conjugates comprising these complexes as a label and their application, e.g. in the electrochemiluminescence based detection of an analyte.
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Page/Page column 16-17
(2012/08/28)
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- Palladium and radical routes to phenanthridines
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Two routes to phenanthridines are reported; a palladium-mediated route using imidoyl-selanides as precursors and a modified radical route using aryl imines as starting materials. ARKAT-USA, Inc.
- Bowman, W. Russell,Lyon, Jessica E.,Pritchard, Gareth J.
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p. 210 - 227
(2013/01/16)
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- Palladium-catalyzed method for the synthesis of carbazoles via tandem C-H functionalization and C-N bond formation
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(Chemical Equation Presented) The development of a new method for the assembly of unsymmetrical carbazoles is reported. The strategy involves the selective intramolecular functionalization of an arene C-H bond and the formation of a new arene C-N bond. The substitution pattern of the carbazole product can be controlled by the design of the biaryl amide substrate, and the method is compatible with a variety of functional groups. The utility of the new protocol was demonstrated by the concise synthesis of three natural products from commercially available materials.
- Tsang, W. C. Peter,Munday, Rachel H.,Brasche, Gordon,Zheng, Nan,Buchwald, Stephen L.
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p. 7603 - 7610
(2008/12/22)
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- Palladium-mediated synthesis of phenanthridines: The first report of palladium insertion into imidoyl selenides
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Imidoyl phenyl selenides have been shown to be precursors to phenanthridines, when treated with Pd(PPh3)4 under reflux in toluene in the presence of a base, giving reasonable yields. It is proposed that insertion of palladium into th
- Bowman, W. Russell,Lyon, Jessica E.,Pritchard, Gareth J.
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scheme or table
p. 2169 - 2171
(2009/04/08)
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- Ortho arylation of acetanilides via Pd(II)-catalyzed C-H functionalization
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A remarkable transformation to realize ortho arylation of acetanilides via Pd(II)-catalyzed C-H functionalization with trialkoxyarylsinaes was demonstrated. Copyright
- Yang, Shangdong,Li, Bijie,Wan, Xiaobing,Shi, Zhangjie
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p. 6066 - 6067
(2008/02/02)
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- SYNTHESE DANS LA SERIE DES PHENANTHRIDINES I. RECHERCHES DES CONDITIONS EXPERIMENTALES OPTIMALES DANS LA PREPARATION D'ALKYL-6 PHENANTHRIDINES ET DE LEUR SEL
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The synthesis of 6-alkylphenanthridines and their corresponding salts has been developed.The well known "biphenyl method" has been studied.Acylation of o-aminobiphenyl is achieved by an acid or the corresponding anhydride or acyl chloride.Cyclization of the intermediate o-acylamidobiphenyl has been studied in various conditions (solvents, temperature...).Quaternization has also been accomplished: new 6-alkylphenanthridinium salts have been prepared in good yields.
- Lion, C.,Boukou-Poba, J. P.,Charvy, C.
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p. 557 - 566
(2007/10/02)
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- Photocyclization of Aryl Halides. Part 3. Phenanthridone Photosynthesis from 2-Halogenobenzanilides
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2-Chlorobenzanilides cyclize to phenanthridones in deaereted cyclohexane solution on 254 nm irradiation, whereas 2-bromo- and 2-iodo-benzanilides undergo dehalogenative reduction.These observations are understandable in terms of the assisted homolysis model as applied to configurationally flexible molecules.Cyclization in hydrocarbon media is retarted by triplet quenchers and fails in polar solvents.The cyclization can also be singlet and triplet sensitized. 4'-Substituents influence the cyclization quantum yield by altering the ?-donor ability of the aniline ring and the rotational barrier about the amide bond.
- Grimshaw, James,Silva, A. Prasanna de
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p. 857 - 866
(2007/10/02)
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- Application of Semmler-Wolff Reaction for the Synthesis of 2-Aminobiphenyls
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Semmler-Wolff reaction of 1-hydroxyimino-2-aryl-2-cyclohexenes (I) yields the corresponding 2-aminobiphenyls (II) in 40-55percent yield.The 2-aminobiphenyls have been fully characterized through spectral data.Further confirmation of the structures of 2-aminobiphenyls is obtained by their conversion to the corresponding phenanthridine derivatives (IV).
- Sivasubramanian, S.,Muthusubramanian, S.,Ramasamy, S.,Arumugam, N
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p. 552 - 554
(2007/10/02)
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- Photocyclisation of 2-Halogenobenzanilides: An Extreme Example of Halogen Atom, Solvent, and Isomer Dependence. A Practical Phenanthridine Synthesis
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2-Chlorobenzanilides photocyclise to phenanthridones by assisted homolysis of the carbon-chlorine bond.
- Grimshaw, James,Silva, A. Prasanna de
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p. 302 - 303
(2007/10/02)
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