- CoPc-catalyzed selective radical arylation of anilines with arylhydrazines for synthesis of 2-aminobiaryls
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CoPc-catalyzed selective radical arylation of anilines with arylhydrazines to afford 2-aminobiaryls in moderate to good yields is described. This journal is the Partner Organisations 2014.
- Jiang, Tao,Chen, Sheng-Yan,Zhang, Guo-Yu,Zeng, Run-Sheng,Zou, Jian-Ping
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- Air-promoted direct radical arylation of anilines with arylhydrazines
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Air-promoted coupling reaction of arylhydrazines and arylamines is developed for the selective synthesis of 2-aminobiaryls. This protocol provides a green, cost-effective, and scale-up method for preparation of 2-aminobiaryls.
- Jiang, Tao,Chen, Sheng-Yan,Zhuang, Huan,Zeng, Run-Sheng,Zou, Jian-Ping
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Read Online
- α-Bromoacrylic Acids as C1 Insertion Units for Palladium-Catalyzed Decarboxylative Synthesis of Diverse Dibenzofulvenes
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Herein α-bromoacrylic acids have been employed as C1 insertion units to achieve the palladium-catalyzed [4 + 1] annulation of 2-iodobiphenyls, which provides an efficient platform for the construction of diverse dibenzofulvenes. This protocol enables the formation of double C(aryl)-C(vinyl) bonds via a C(vinyl)-Br bond cleavage and decarboxylation. It is particularly noteworthy that the method features a broad substrate scope, and various interesting frameworks, such as bridged ring, fused (hetero)aromatic ring, and divinylbenzene, can be successfully incorporated into the products.
- Zhang, Minghao,Deng, Wenbo,Sun, Mingjie,Zhou, Liwei,Deng, Guobo,Liang, Yun,Yang, Yuan
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supporting information
p. 5744 - 5749
(2021/08/18)
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- Catalytic enantioselective synthesis of chiral spirocyclic 1,3-diketones: Via organo-cation catalysis
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An SPA-triazolium bromide-catalyzed transannular C-acylation of enol lactones is presented. This methodology provides convenient access to a range of enantioenriched spirocyclic 1,3-diketones in moderate to high yields and enantioselectivities and features a broad substrate scope in terms of enol lactones. The catalytic capability of this triazolium salt catalyst is also demonstrated in this enantioselective transformation, which could inspire its further application. This journal is
- Zhang, Xiao-Yan,Shao, Ya-Ping,Guo, Bao-Kuan,Zhang, Kun,Zhang, Fu-Min,Zhang, Xiao-Ming,Tu, Yong-Qiang
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supporting information
p. 11233 - 11235
(2021/11/09)
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- Asymmetric palladium complex, preparation method and application thereof in catalysis of olefin polymerization
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The invention belongs to the technical field of chemical synthesis, and particularly relates to an asymmetric palladium complex, a preparation method and application thereof in catalysis of olefin polymerization. According to the asymmetric alpha-diimine palladium complex disclosed by the invention, a rigid camphanyl skeleton with large steric hindrance is adopted, so that the axial steric hindrance effect of a catalyst can be improved, and the thermal stability and polymerization activity of the catalyst are further improved; aniline with only one phenyl substituted ortho-position is adopted, and the other ortho-position (6-position) has no substituent, so that the coordination of olefin substituted by large steric hindrance is facilitated, and the catalytic activity is improved; in addition, the complex is simple to synthesize and high in yield, has wide adaptability to polymerization of large-steric-hindrance substituted olefin, and has high economic value.
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Paragraph 0021; 0046-0048
(2021/06/06)
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- 4CzIPN-tBu-Catalyzed Proton-Coupled Electron Transfer for Photosynthesis of Phosphorylated N-Heteroaromatics
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2,4,5,6-Tetrakis(3,6-di-tert-butyl-9H-carbazol-9-yl)isophthalonitrile (4CzIPN-tBu) was developed as a photocatalyst for the phosphorus-radical-initiated cascade cyclization reaction of isocyanides. By using 4CzIPN-tBu as catalyst, we developed a visible-light-induced proton-coupled electron transfer strategy for the generation of phosphorus-centered radicals, via which a wide range of phosphorylated phenanthridines, quinolines, and benzothiazoles were successfully constructed.
- Liu, Yan,Chen, Xiao-Lan,Li, Xiao-Yun,Zhu, Shan-Shan,Li, Shi-Jun,Song, Yan,Qu, Ling-Bo,Yu, Bing
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supporting information
p. 964 - 972
(2021/01/12)
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- Scalable electrochemical synthesis of diaryliodonium salts
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Cyclic and acyclic diaryliodonium are synthesised by anodic oxidation of iodobiaryls and iodoarene/arene mixtures, respectively, in a simple undivided electrolysis cell in MeCN-HFIP-TfOH without any added electrolyte salts. This atom efficient process does not require chemical oxidants and generates no chemical waste. More than 30 cyclic and acyclic diaryliodonium salts with different substitution patterns were prepared in very good to excellent yields. The reaction was scaled-up to 10 mmol scale giving more than four grams of dibenzo[b,d]iodol-5-ium trifluoromethanesulfonate (>95%) in less than three hours. The solvent mixture of the large-scale experiment was recovered (>97%) and recycled several times without significant reduction in yield.
- Elsherbini, Mohamed,Moran, Wesley J.
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supporting information
p. 4706 - 4711
(2021/06/11)
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- Direct photoexcitation of benzothiazolines: Acyl radical generation and application to access heterocycles
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An acyl radical generation and functionalization strategy through direct photoexcitation of benzothiazolines has been developed. The formed acyl radical species can either be trapped by quinoxalin-2-ones to realize their C(3)-H functionalization or trigger a cascade radical cyclization with isonitriles to synthesise biologically important phenanthridines. The synthetic value of this protocol can be further illustrated by the modification of quinoxalin-2-ones, containing important natural products and drug-based complex molecules.
- He, Xiang-Kui,Li, Lei,Lu, Juan,Xuan, Jun,Ye, Hai-Bing
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supporting information
(2021/11/27)
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- Visible-Light-Induced Decarboxylative Cyclization/Hydrogenation Cascade Reaction to Access Phenanthridin-6-yl(aryl)methanol by an Electron Donor-Acceptor Complex
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A novel and efficient visible-light-induced decarboxylative cyclization/hydrogenation cascade reaction of α-oxocarboxylic acids and 2-isocyanobiaryls has been developed. Without the need of any external photosensitizer, oxidant, and reductant, this method offers a mild and green approach for the synthesis of diverse alcohols in moderate to good yields. A mechanism indicated that an electron donor-acceptor complex-driven decarboxylation, radical addition/cyclization, and in situ photochemical reduction of ketones to alcohols could be involved in the reaction.
- Shi, Wei,Ma, Fang,Li, Pinhua,Wang, Lei,Miao, Tao
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p. 13808 - 13817
(2020/11/20)
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- Regiospecific Introduction of Halogens on the 2-Aminobiphenyl Subunit Leading to Highly Potent and Selective M3 Muscarinic Acetylcholine Receptor Antagonists and Weak Inverse Agonists
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Muscarinic M3 receptor antagonists and inverse agonists displaying high affinity and subtype selectivity over the antitarget M2 are valuable pharmacological tools and may enable improved treatment of chronic obstructive pulmonary disease (COPD), asthma, or urinary incontinence. On the basis of known M3 antagonists comprising a piperidine or quinuclidine unit attached to a biphenyl carbamate, 5-fluoro substitution was responsible for M3 subtype selectivity over M2, while 3′-chloro substitution substantially increased affinity through a σ-hole interaction. Resultantly, two piperidinyl-and two quinuclidinium-substituted biphenyl carbamates OFH243 (13n), OFH244 (13m), OFH3911 (14n), and OFH3912 (14m) were discovered, which display two-digit picomolar affinities with Ki values from 0.069 to 0.084 nM, as well as high selectivity over the M2 subtype (46-to 68-fold). While weak inverse agonistic properties were determined for the biphenyl carbamates 13m and 13n, neutral antagonism was observed for 14m and 14n and tiotropium under identical assay conditions.
- Fischer, Oliver,Hofmann, Josefa,Rampp, Hannelore,Kaindl, Jonas,Pratsch, Gerald,Bartuschat, Amelie,Taudte, R. Verena,Fromm, Martin F.,Hübner, Harald,Gmeiner, Peter,Heinrich, Markus R.
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p. 4349 - 4369
(2020/06/08)
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- Regiospecific Introduction of Halogens on the 2-Aminobiphenyl Subunit Leading to Highly Potent and Selective M3 Muscarinic Acetylcholine Receptor Antagonists and Weak Inverse Agonists
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Muscarinic M3 receptor antagonists and inverse agonists displaying high affinity and subtype selectivity over the antitarget M2 are valuable pharmacological tools and may enable improved treatment of chronic obstructive pulmonary disease (COPD), asthma, or urinary incontinence. On the basis of known M3 antagonists comprising a piperidine or quinuclidine unit attached to a biphenyl carbamate, 5-fluoro substitution was responsible for M3 subtype selectivity over M2, while 3′-chloro substitution substantially increased affinity through a σ-hole interaction. Resultantly, two piperidinyl- A nd two quinuclidinium-substituted biphenyl carbamates OFH243 (13n), OFH244 (13m), OFH3911 (14n), and OFH3912 (14m) were discovered, which display two-digit picomolar affinities with Ki values from 0.069 to 0.084 nM, as well as high selectivity over the M2 subtype (46-to 68-fold). While weak inverse agonistic properties were determined for the biphenyl carbamates 13m and 13n, neutral antagonism was observed for 14m and 14n and tiotropium under identical assay conditions.
- Fischer, Oliver,Hofmann, Josefa,Rampp, Hannelore,Kaindl, Jonas,Pratsch, Gerald,Bartuschat, Amelie,Taudte, R. Verena,Fromm, Martin F.,Hübner, Harald,Gmeiner, Peter,Heinrich, Markus R.
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p. 4349 - 4369
(2020/06/08)
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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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- NBE-Controlled Palladium-Catalyzed Interannular Selective C-H Silylation: Access to Divergent Silicon-Containing 1,1′-Biaryl-2-Acetamides
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A novel palladium-catalyzed interannular selective C-H silylation of 1,1′-biaryl-2-acetamides is described. The combination of palladium catalyst with copper oxidant enables meta- or ortho-selective C-H silylation by employing hexamethyldisilane as a trimethylsilyl source, which relies on the control of NBE derivatives as a switch, thus providing straightforward access to divergent silicon-containing 1,1′-biaryl-2-acetamides.
- Li, Wenguang,Chen, Wenqi,Zhou, Bang,Xu, Yankun,Deng, Guobo,Liang, Yun,Yang, Yuan
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supporting information
p. 2718 - 2722
(2019/04/16)
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- Cobalt(II)-Catalyzed [5+2] C?H Annulation of o-Arylanilines with Alkynes: An Expedient Route to Dibenzo-[b,d]azepines
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The first example of CoCl2-catalyzed formal [5+2] oxidative annulation of o-arylanilines with alkynes was developed, giving access to various important imine-containing dibenzo-[b,d]azepine scaffolds through sequential C?C/C?N bond formation. The reaction employs catalytic amount of manganese and oxygen as cooxidants, and features a broad substrate scope. Preliminary mechanistic studies suggested that C?H activation is involved in the rate-determining step. Moreover, both internal and terminal alkynes are well tolerated in this transformation. Besides, a regioselective migratory insertion was observed when using terminal alkynes as substrates. (Figure presented.).
- Ling, Fei,Xie, Zhen,Chen, Jiachen,Ai, Chongren,Shen, Haiwei,Wang, Ze,Yi, Xiao,Zhong, Weihui
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supporting information
p. 3094 - 3101
(2019/05/21)
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- Rhodium(I)-Catalyzed Aryl C-H Carboxylation of 2-Arylanilines with CO2
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An unprecedented Rh(I)-catalyzed, amino-group-assisted C-H carboxylation of 2-arylanilines with CO2 under redox-neutral conditions has been developed. This reaction was promoted by a phosphine ligand with t-BuOK as the base and did not require the use of additional strong organometallic reagent. It enabled an efficient direct conversion of a broad range of 2-(hetero)arylanilines including electron-deficient heteroarenes to various phenanthridinones. Possible intermediates of the reaction were also evaluated in the preliminary mechanistic studies.
- Gao, Yuzhen,Cai, Zhihua,Li, Shangda,Li, Gang
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supporting information
p. 3663 - 3669
(2019/05/17)
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- Visible-light-induced tandem radical addition-cyclization of 2-aryl phenyl isocyanides catalysed by recyclable covalent organic frameworks
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A visible-light-induced tandem radical addition-cyclization sequence via 2-aryl phenyl isocyanides as the starting material and two-dimensional covalent organic frameworks (2D-COFs) as the photocatalyst was developed, delivering multifarious 6-substituted phenanthridines in high yields. Benefitting from the utilization of a heterogeneous photocatalyst, this protocol features easy catalyst separation and excellent recyclability. A negligible loss of the catalytic activity was observed after multiple runs. High practicability of this protocol was further demonstrated by continuous flow experiments.
- Liu, Shuyang,Pan, Wenna,Wu, Songxiao,Bu, Xiubin,Xin, Shigang,Yu, Jipan,Xu, Hao,Yang, Xiaobo
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supporting information
p. 2905 - 2910
(2019/06/17)
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- Synthesis, Isolation, and Characterization of Mono- and Bis-norbornene-Annulated Biarylamines through Pseudo-Catellani Intermediates
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A palladium-catalyzed C-H functionalization of an external ring of N-acyl 2-aminobiaryl with bicyclo[2.2.1]hept-2-ene (norbornene) via multiple C-H bond activations was developed. This study is the first report of the formation of bis-norbornene annulated biarylamines isomers (syn-3a′/anti-3a′ = 36:64) from multiple C-H bond functionalizations. Additionally, nondirected C-H bond functionalization at the C-4′ position with alkenes rendered complete C-H functionalization of five C-H bonds that formed a stable hexasubstituted benzene ring.
- Annamalai, Pratheepkumar,Hsiao, Huan-Chang,Raju, Selvam,Fu, Yi-Hsuan,Chen, Pei-Ling,Horng, Jia-Cherng,Liu, Yi-Hung,Chuang, Shih-Ching
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supporting information
p. 1182 - 1186
(2019/02/14)
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- Metal-Oxidant-Free Cobalt-Catalyzed C(sp2)-H Carbonylation of ortho-Arylanilines: An Approach toward Free (NH)-Phenanthridinones
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A traceless directing group assisted Co-catalyzed C(sp2)-H carbonylation of ortho-arylanilines for the synthesis of free (NH)-phenanthridinones in metal-based-oxidant-free fashion was accomplished. This protocol employs diisopropyl azodicarboxylate as the CO source and oxygen as the sole oxidant, and provides good yields with various functional tolerance. The methodology has been applied for the total synthesis of PARP inhibitor PJ-34. Furthermore, the kinetic isotopic effect experiments reveal the C-H bond cleavage probably occurred in the rate-determining step.
- Ling, Fei,Zhang, Chaowei,Ai, Chongren,Lv, Yaping,Zhong, Weihui
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p. 5698 - 5706
(2018/05/23)
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- Palladium/Norbornene Chemistry: Synthesis of Norbornene-Containing Arylsilanes Involving Double C-Si Bond Formation
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A novel palladium-catalyzed three-component cascade reaction of aryl halides with norbornene and hexamethyldisilane has been described, which allows the simultaneous construction of two C-Si bonds and one C-C bond. The method achieves ortho C-H functionalization of aryl halides through the formation of the five-membered palladacycle, leading to norbornene-containing arylsilanes.
- Xu, Yankun,Liu, Xiaodong,Chen, Wenqi,Deng, Guobo,Liang, Yun,Yang, Yuan
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p. 13930 - 13939
(2018/11/30)
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- Electrochemical initiation of electron-catalyzed phenanthridine synthesis by trifluoromethylation of isonitriles
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The electron-catalyzed formation of phenanthridines starting from isonitriles initiated by an electrochemical reduction of the Togni reagent is presented. The required number of faradays per mole of starting material and the respective yields clearly show the catalytic character of the electron in this reaction. The mechanism is supported by cyclic voltammetry experiments.
- Lübbesmeyer,Leifert,Sch?fer,Studer
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supporting information
p. 2240 - 2243
(2018/03/06)
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- Visible-light-promoted intramolecular C-H amination in aqueous solution: Synthesis of carbazoles
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An effective and operationally simple protocol is reported for the synthesis of versatile carbazoles. With water as a co-solvent, visible-light rather than various metals is used to facilitate the conversion of readily available 2-azidobiphenyls under mild conditions. Various functionalized bioactive natural alkaloids, such as glycoborine, clausine C, clausine L, clausine H and clauszoline K, were synthesized efficiently with nitrogen as a sole byproduct. The reaction could be performed in water, acidic or alkaline buffer solutions, showing its potential for applications in biochemistry.
- Yang, Lizheng,Zhang, Yipin,Zou, Xiaodong,Lu, Hongjian,Li, Guigen
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supporting information
p. 1362 - 1366
(2018/03/26)
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- The use of the arylhydrazine synthetic amino of the biphenyl method
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The present invention describes a method for synthesising 2-aminobiphenyls and derivatives thereof. This method can be performed cost-effectively and is based on selective reactions. Functionalised biphenyl compounds are of great interest, particularly as pharmaceuticals and agricultural chemicals, and as precursors for such active ingredients. The method for producing a compound of formula 3 is characterised in that a compound of formula 1 is reacted with a compound of formula 2 in the presence of an oxidising agent.
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Paragraph 0228; 0363-0365
(2017/10/28)
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- Pd/Cu-Catalyzed aerobic oxidative aromatic C-H bond activation/N-dealkylative carbonylation towards the synthesis of phenanthridinones
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It is important to achieve diverse functionalization of tertiary anilines due to their importance in biological molecules, pharmaceutical, functional materials, and ligands. A straightforward Pd/Cu-catalyzed oxidative C-H bond activation/N-dealkylative carbonylation of tertiary [1,1′-biphenyl]-2-anilines towards the synthesis of various biologically important phenanthridin-6(5H)-ones has been developed. A wide range of functional groups are well tolerated in this transformation. Moreover, O2 is utilized as the terminal oxidant to promote the oxidative carbonylation process.
- Shi, Renyi,Niu, Huiying,Lu, Lijun,Lei, Aiwen
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p. 1908 - 1911
(2017/02/10)
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- Ruthenium-Catalyzed Enantioselective Hydrogenation of Phenanthridine Derivatives
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The first asymmetric hydrogenation of phenanthridines catalyzed by chiral cationic ruthenium diamine complexes has been developed with up to 92% ee and full conversions. The choice of the counteranion of the catalyst was found to be critical for achieving high enantioselectivity. In addition, the obtained 5,6-dihydrophenanthridine could be used as a chiral hydride donor for organocatalytic asymmetric transfer hydrogenation.
- Yang, Zhusheng,Chen, Fei,Zhang, Shuxin,He, Yanmei,Yang, Nianfa,Fan, Qing-Hua
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supporting information
p. 1458 - 1461
(2017/03/23)
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- Extended Study of Visible-Light-Induced Photocatalytic [4 + 2] Benzannulation: Synthesis of Polycyclic (Hetero)Aromatics
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Herein we report an extended study of [4 + 2] benzannulation reactions of 2-(hetero)aryl-substituted anilines with alkynes by visible light photocatalysis. The method requires the use of tBuONO as a diazotizing agent and 0.3 mol % of fac-Ir(ppy)3 as a photocatalyst at room temperature. The reaction proceeded in a chemo- and regioselective manner with high functional group tolerance under mild conditions allowing the preparation of a wide variety of polycyclic (hetero)aromatic compounds, including phenanthrenes, in moderate to high yields. This procedure is amenable to gram-scale synthesis of 9-phenylphenanthrene.
- Chatterjee, Tanmay,Lee, Da Seul,Cho, Eun Jin
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p. 4369 - 4378
(2017/04/28)
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- Palladium-Catalyzed C-H Bond Activation by Using Iminoquinone as a Directing Group and an Internal Oxidant or a Co-oxidant: Production of Dihydrophenanthridines, Phenanthridines, and Carbazoles
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A palladium-catalyzed C-H bond activation reaction, via a redox-neutral pathway, for the preparation of dihydrophenanthridine, phenanthridine, and carbazole derivatives from biaryl 2-iminoquinones is developed. The preinstalled iminoquinone was designed to act as a directing group for ortho C-H activation and an internal oxidant or a co-oxidant. This catalysis proceeded through the following sequence: C-H bond activation, coordination and insertion of activated olefins, β-hydride elimination, H-shift, insertion, and protonation or β-hydride elimination. In addition, carbazoles can be prepared efficiently by using this method without the addition of external oxidants.
- Raju, Selvam,Annamalai, Pratheepkumar,Chen, Pei-Ling,Liu, Yi-Hung,Chuang, Shih-Ching
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supporting information
p. 4134 - 4137
(2017/08/15)
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- Synthesis of Fluorenes Starting from 2-Iodobiphenyls and CH2Br2 through Palladium-Catalyzed Dual C-C Bond Formation
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A facile and efficient approach is developed for the synthesis of fluorene and its derivatives starting from 2-iodobiphenyls and CH2Br2. A range of fluorene derivatives can be synthesized under relatively mild conditions. The reaction proceeds via a tandem palladium-catalyzed dual C-C bond formation sequence through the key dibenzopalladacyclopentadiene intermediates, which are obtained from 2-iodobiphenyls through palladium-catalyzed C-H activation.
- Shi, Guangfa,Chen, Dushen,Jiang, Hang,Zhang, Yu,Zhang, Yanghui
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supporting information
p. 2958 - 2961
(2016/07/06)
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- Synthesis of Triphenylenes Starting from 2-Iodobiphenyls and Iodobenzenes via Palladium-Catalyzed Dual C-H Activation and Double C-C Bond Formation
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A novel and facile approach for the synthesis of triphenylenes has been developed via palladium-catalyzed coupling of 2-iodobiphenyls and iodobenzenes. The reaction involves dual palladium-catalyzed C-H activations and double palladium-catalyzed C-C bond formations. A range of unsymmetrically functionalized triphenylenes can be synthesized with the reaction. The approach features readily available starting materials, high atom- and step-economy, and access to various unsymmetrically functionalized triphenylenes.
- Zhang, Yanghui,Pan, Shulei,Jiang, Hang,Zhang, Yu,Chen, Dushen
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supporting information
p. 5192 - 5195
(2016/11/02)
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- Silver-catalyzed oxidative decarboxylation of difluoroacetates: Efficient access to C-CF2 bond formation
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A mild, versatile and efficient method for the silver(i)-catalyzed oxidative decarboxylative gem-difluoromethylenation has been developed. The radical cascade reaction comprises the addition of an oxidatively generated difluoromethylene radical to the isonitrile functionality and subsequent homolytic aromatic substitution. It provides a novel and efficient access to the C-CF2 bond formation.
- Wan, Wen,Ma, Guobin,Li, Jialiang,Chen, Yunrong,Hu, Qingyang,Li, Minjie,Jiang, Haizhen,Deng, Hongmei,Hao, Jian
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supporting information
p. 1598 - 1601
(2016/01/30)
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- Iron-Catalyzed Intramolecular C(sp2)-H Amination
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The nucleophilic iron complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) catalyzes the direct intramolecular C-H amination of α-azidobiaryls and (azidoaryl)alkenes into the corresponding carbazoles and indoles, respectively, under mild conditions and with low catalyst loadings. These features and the broad functional-group tolerance render this method a particularly attractive alternative to established noble-metal-based procedures.
- Alt, Isabel T.,Plietker, Bernd
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supporting information
p. 1519 - 1522
(2016/02/14)
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- MeOTf- and TBD-Mediated Carbonylation of ortho-Arylanilines with CO2 Leading to Phenanthridinones
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Carbonylation of o-arylanilines utilizing CO2 as a carbonyl source for the synthesis of important phenanthridinones with a free (NH)-lactam motif has been described under metal-free condition. A range of o-arylanilines were transformed to the corresponding phenanthridinones in high yields.
- Wang, Sheng,Shao, Peng,Du, Gaixia,Xi, Chanjuan
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p. 6672 - 6676
(2016/08/16)
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- Palladium-Catalyzed Intramolecular C–H Amination in Water
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Palladium(II) catalysis was found to be effective for intramolecular C–H amination in water. With 2-azidobiphenyls as substrates, the reaction efficiently provided various carbazoles with N2as the sole byproduct. The reaction showed high functional-group tolerance and could be used in the synthesis of several natural carbazole alkaloids. The catalytic process was promoted by water, and the reaction was inefficient in the organic solvents that were investigated.
- Yang, Lizheng,Li, Hao,Zhang, Haifei,Lu, Hongjian
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supporting information
p. 5611 - 5615
(2016/12/14)
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- Transition-metal-free synthesis of phenanthridinones from biaryl-2-oxamic acid under radical conditions
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Na2S2O8-promoted decarboxylative cyclization of biaryl-2-oxamic acid for phenanthridinones has been developed. This work illustrates the first example of intramolecular decarboxylative amidation of unactivated arene under transition-metal-free conditions. Additionally, this approach provides an efficient and economical method to access biologically interesting phenanthridinones, an important structure motif in many natural products. (Chemical Equation Presented).
- Yuan, Ming,Chen, Li,Wang, Junwei,Chen, Shenjie,Wang, Kongchao,Xue, Yongbo,Yao, Guangmin,Luo, Zengwei,Zhang, Yonghui
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supporting information
p. 346 - 349
(2015/02/19)
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- Photoredox-Catalyzed Tandem Insertion/Cyclization Reactions of Difluoromethyl and 1,1-Difluoroalkyl Radicals with Biphenyl Isocyanides
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Using visible-light photoredox conditions, difluoromethylation and 1,1-difluoroalkylation of biphenyl isocyanides have allowed the synthesis of a series of 6-(difluoromethyl)- and 6-(1,1-difluoroalkyl)phenanthridines via tandem addition/cyclization/oxidation processes. The reactions are carried out in wet dioxane at room temperature using fac-Ir(ppy)3 as catalyst to form a large variety of substituted phenanthridine products in good to excellent yield.
- Zhang, Zuxiao,Tang, Xiaojun,Dolbier, William R.
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supporting information
p. 4401 - 4403
(2015/09/28)
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- Oxidative radical arylation of anilines with arylhydrazines and dioxygen from air
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Substituted 2-aminobiphenyls have been prepared from arylhydrazine hydrochlorides and anilines in biphasic radical arylation reactions with dioxygen from air as a most simple and readily available oxidant. Under optimized conditions, the free amino functionality of the aniline leads to high ortho:meta regioselectivities, now even for anilines bearing a donor substituent in the para position. Finally, the mild and metal-free new access to aminobiphenyls was shown to be applicable on a gram scale.
- Hofmann, Josefa,Jasch, Hannelore,Heinrich, Markus R.
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p. 2314 - 2320
(2014/04/03)
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- Co(acac)2/O2-mediated oxidative isocyanide insertion with 2-aryl anilines: Efficient synthesis of 6-amino phenanthridine derivatives
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A novel and efficient protocol for the creation of 6-amino phenanthridine derivatives by Co(acac)2-catalyzed isocyanide insertion with 2-aryl anilines under an O2 atmosphere via homolytic aromatic substitution (HAS) type C-H functionalization has been developed. This reaction not only proceeds smoothly utilizing O2 as the oxidant but also provides a new approach to construct phenanthridine derivatives utilizing readily available 2-aryl anilines with isocyanides instead of 2-isocyanobiaryls with different radical precursors.
- Zhu, Tong-Hao,Wang, Shun-Yi,Tao, Yang-Qing,Wei, Tian-Qi,Ji, Shun-Jun
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supporting information
p. 1260 - 1263
(2014/03/21)
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- PLATINUM COMPOUNDS, COMPOSITIONS AND METHODS FOR THE TREATMENT OF CANCER
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The present disclosure relates to novel pharmaceutical compositions comprising a nanoparticle associated with, tether to, or encapsulating a platinum-based active pharmaceutical agent. The platinum-based drug is released from the nanoparticles in a controlled fashion. Also contemplated are methods of making the nanoparticles, as well as methods for using them in the treatment or prevention of diseases or conditions. One embodiment relates to phenanthriplatin nanoparticles and methods of using and making the same.
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Paragraph 00239
(2014/04/03)
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- Synthesis of phenanthridine derivatives via cascade annulation of diaryliodonium salts and nitriles
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A cascade coupling reaction toward a variety of phenanthridine derivatives has been developed. This cascade transformation proceeds via the copper-catalyzed coupling reaction of diaryliodonium salts and nitriles, and undergoes cyclization into the phenanthridine core.
- Li, Jian,Wang, Hongni,Sun, Jiangtao,Yang, Yang,Liu, Li
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supporting information
p. 7904 - 7908
(2014/12/12)
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- Process for the Synthesis of Aminobiphenylene
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The present invention relates to a process for the synthesis of 2-aminobiphenylene and derivatives thereof by reacting a benzene diazonium salt with an aniline compound under basic reaction conditions.
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Paragraph 0243; 0244; 0282; 0283; 0284; 0285; 0286-0289
(2014/02/15)
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- 6-Aroylated phenanthridines via base promoted homolytic aromatic substitution (BHAS)
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Readily accessible 2-isocyanobiphenyls react with aromatic aldehydes via base promoted homolytic aromatic substitution (BHAS) to give 6-aroylated phenanthridines. Reactions occur via addition of acyl radicals to the isonitrile functionality and subsequent intramolecular BHAS of the intermediate imidoyl radicals. Initiation of the radical chain reaction is best achieved with small amounts of FeCl3 (0.4 mol %), and the commercially available and cheap tBuOOH is used as the oxidant.
- Leifert, Dirk,Daniliuc, Constantin Gabriel,Studer, Armido
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supporting information
p. 6286 - 6289
(2014/01/17)
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- Free-amine directed arylation of biaryl-2-amines with aryl iodides by palladium catalysis
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A new palladium-catalyzed free-amine directed arylation of C(sp 2)-H bonds in the presence of AgOAc and TFA is described. Biaryl-2-amines react with various aryl iodides to give the corresponding mono- or diarylated products with exclusive regioselectivity.
- Liang, Zunjun,Feng, Ruokun,Yin, Hong,Zhang, Yuhong
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supporting information
p. 4544 - 4547
(2013/09/24)
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- Pd(II)-catalyzed C(sp2)-H carbonylation of biaryl-2-amine: Synthesis of phenanthridinones
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A Pd(OAc)2-catalyzed C(sp2)-H carbonylation protocol of arenes under carbon monoxide atmosphere has been developed. The scope of the carbonylation reaction is broad and tolerates a variety of useful functional groups. This reaction provides a novel and efficient method for the synthesis of biologically and pharmaceutically significant phenanthridinones.
- Liang, Zunjun,Zhang, Jitan,Liu, Zhanxiang,Wang, Kai,Zhang, Yuhong
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p. 6519 - 6526
(2013/07/26)
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- 6-Trifluoromethyl-phenanthridines through radical trifluoromethylation of isonitriles
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A radical approach toward 6-perfluoroalkylphenanthridines employs the Togni reagent or derivatives thereof as radical precursors and occurs in the absence of a transition metal. Bu4NI is applied as radical initiator and phenanthridines are formed in good to excellent yields. In contrast to the currently intensively investigated trifluoromethylation of arenes, the arene core is formed during the trifluoromethylation in this approach. Copyright
- Zhang, Bo,Mueck-Lichtenfeld, Christian,Daniliuc, Constantin Gabriel,Studer, Armido
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supporting information
p. 10792 - 10795
(2013/10/22)
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- The gomberg-bachmann reaction for the arylation of anilines with aryl diazotates
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Simply aqueous sodium hydroxide is sufficient to exclude ionic side reactions and to prepare 2-aminobiphenyls from aryl diazotates and anilines through a new variant of the Gomberg-Bachmann reaction (see scheme). The metal-free reaction under basic conditions allows to exploit the highly radical-stabilizing effect of the aniline's free amino function for the first time, which leads to a so far unreached regioselectivity. Copyright
- Pratsch, Gerald,Wallaschkowski, Tina,Heinrich, Markus R.
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supporting information
p. 11555 - 11559,5
(2012/12/12)
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- The gomberg-bachmann reaction for the arylation of anilines with aryl diazotates
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Simply aqueous sodium hydroxide is sufficient to exclude ionic side reactions and to prepare 2-aminobiphenyls from aryl diazotates and anilines through a new variant of the Gomberg-Bachmann reaction (see scheme). The metal-free reaction under basic conditions allows to exploit the highly radical-stabilizing effect of the aniline's free amino function for the first time, which leads to a so far unreached regioselectivity. Copyright
- Pratsch, Gerald,Wallaschkowski, Tina,Heinrich, Markus R.
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supporting information
p. 11555 - 11559
(2013/01/14)
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- Modular synthesis of phenanthridine derivatives by oxidative cyclization of 2-isocyanobiphenyls with organoboron reagents
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Where HAS you been? A manganese-mediated annulation of 2-isocyanobiaryls with organoboronic acids is developed for the synthesis of a broad range of phenanthridine derivatives (see scheme). Mechanistic studies indicate that the reaction proceeds by the intramolecular homolytic aromatic substitution (HAS) of an imidoyl radical intermediate. Copyright
- Tobisu, Mamoru,Koh, Keika,Furukawa, Takayuki,Chatani, Naoto
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supporting information
p. 11363 - 11366
(2013/01/15)
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- Free-amine-directed alkenylation of C(sp2)-H and cycloamination by palladium catalysis
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A new protocol for the palladium-catalyzed free-amine-directed alkenylation of C(sp2)-H bonds and cycloamination is described. Substituted biaryl-2-amines react with various alkenes, including electron-deficient alkenes, aryl alkenes and alkyl alkenes, to give the corresponding phenanthridines with exclusive regioselectivity. The use of α-branched styrenes leads to the formation of tricyclic compounds with a seven-membered amine ring. The method operates through a free-amine-directed alkenylation and a subsequent hydroamination cyclization reaction. Seven-membered cycloamination: A new protocol for the palladium-catalyzed free-amine-directed alkenylation of C(sp2)-H bonds and subsequent cycloamination is described (see scheme). Substituted biaryl-2-amines react with various alkenes to give the corresponding phenanthridines with exclusive regioselectivity. The use of α-branched styrenes leads to the formation of tricyclic compounds with a seven-membered amine ring. Copyright
- Liang, Zunjun,Ju, Long,Xie, Yongju,Huang, Lehao,Zhang, Yuhong
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supporting information
p. 15816 - 15821
(2013/01/16)
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- Intramolecular oxidative C-N bond formation for the synthesis of carbazoles: Comparison of reactivity between the copper-catalyzed and metal-free conditions
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New synthetic procedures for intramolecular oxidative C-N bond formation have been developed for the preparation of carbazoles starting from N-substituted amidobiphenyls under either Cu-catalyzed or metal-free conditions using hypervalent iodine(III) as an oxidant. Whereas iodobenzene diacetate or bis(trifluoroacetoxy)iodobenzene alone undergoes the reaction to provide carbazole products in moderate to low yields, combined use of copper(II) triflate and the iodine(III) species significantly improves the reaction efficiency, giving a more diverse range of products in good to excellent yields. On the basis of mechanistic studies including kinetic profile, isotope effects, and radical inhibition experiments, the copper species is proposed to catalytically activate the hypervalent iodine(III) oxidants. The synthetic utility of the present approach was nicely demonstrated in a direct synthesis of indolo[3,2-b]carbazole utilizing a double C-N bond formation.
- Cho, Seung Hwan,Yoon, Jungho,Chang, Sukbok
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supporting information; experimental part
p. 5996 - 6005
(2011/06/11)
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- Rh2(II)-catalyzed synthesis of carbazoles from biaryl azides
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An array of carbazoles (23 examples) can be synthesized from substituted biaryl azides at 60 °C using substoichio-metric quantities of Rh 2(O2CC3F7)4 or Rh 2(O2CC7H15)4.
- Stokes, Benjamin J.,Jovanovic, Brankica,Dong, Huijun,Richert, Kathleen J.,Riell, Ryan D.,Driver, Tom G.
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supporting information; experimental part
p. 3225 - 3228
(2009/08/07)
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