- Accessing Unsymmetrically Linked Heterocycles through Stereoselective Palladium-Catalyzed Domino Cyclization
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A palladium-catalyzed strategy is presented to synthesize unsymmetrically linked heterocycles within stereoselective tetrasubstituted olefins. This reaction is proposed to occur via a vinyl-PdII intermediate capable of initiating the cyclizatio
- Arora, Ramon,Lautens, Mark,Rodríguez, José F.,Whyte, Andrew
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supporting information
(2021/12/09)
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- Acid-Promoted Expeditious Syntheses of Aminated Dibenzosultams via Palladium/Norbornene Cooperatively Catalysed C?H Amination/Arylation
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Herein we reported a protocol to access aminated benzofused sultams through sequential ortho-amination, followed by ipso-arylation of aryl iodide bearing sulfonamide functional group via palladium/norbornene coorperative catalysis. This reaction has showcased a broad spectrum of substrate scope under mild conditions with moderate to good efficiency. (Figure presented.).
- Zhao, Shen,Han, Shibo,Du, Guopeng,Zhang, Daopeng,Liu, Hui,Li, Xinjin,Dong, Yunhui,Sun, Feng-Gang
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p. 2078 - 2083
(2021/03/01)
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- Ruthenium(ii) complexes with N-heterocyclic carbene-phosphine ligands for theN-alkylation of amines with alcohols
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Metal hydride complexes are key intermediates forN-alkylation of amines with alcohols by the borrowing hydrogen/hydrogen autotransfer (BH/HA) strategy. Reactivity tuning of metal hydride complexes could adjust the dehydrogenation of alcohols and the hydrogenation of imines. Herein we report ruthenium(ii) complexes with hetero-bidentate N-heterocyclic carbene (NHC)-phosphine ligands, which realize smart pathway selection in theN-alkylated reactionviareactivity tuning of [Ru-H] species by hetero-bidentate ligands. In particular, complex6cbwith a phenyl wingtip group and BArF?counter anion, is shown to be one of the most efficient pre-catalysts for this transformation (temperature is as low as 70 °C, neat conditions and catalyst loading is as low as 0.25 mol%). A large variety of (hetero)aromatic amines and primary alcohols were efficiently converted into mono-N-alkylated amines in good to excellent isolated yields. Notably, aliphatic amines, challenging methanol and diamines could also be transformed into the desired products. Detailed control experiments and density functional theory (DFT) calculations provide insights to understand the mechanism and the smart pathway selectionvia[Ru-H] species in this process.
- Huang, Ming,Li, Yinwu,Lan, Xiao-Bing,Liu, Jiahao,Zhao, Cunyuan,Liu, Yan,Ke, Zhuofeng
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supporting information
p. 3451 - 3461
(2021/05/03)
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- Photoinduced [3+2] Annulation of Alkene with o-Iodoanilines: An Expedient Approach to Indolines
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A highly regioselective [3+2] cyclization of alkenes with 2-iodoanilines under the irradiation of UV light is described. This general, metal-free strategy facilitates the direct preparation of 2-mono-/disubstituted indolines as well as spiroindolines through alkene carboamination in one step. Mechanistic studies suggested that the photochemical protocol proceeded via a radical pathway.
- Zhao, Xinxin,Guo, Lin,Yang, Chao,Xia, Wujiong
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supporting information
p. 1341 - 1348
(2020/11/19)
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- Modular counter-Fischer?indole synthesis through radical-enolate coupling
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A single-electron transfer mediated modular indole formation reaction from a 2-iodoaniline derivative and a ketone has been developed. This transition-metal-free reaction shows a broad substrate scope and unconventional regioselectivity trends. Moreover, important functional groups for further transformation are tolerated under the reaction conditions. Density functional theory studies reveal that the reaction proceeds by metal coordination, which converts a disfavored 5-endo-trig cyclization to an accessible 7-endo-trig process.
- Chung, Hyunho,Kim, Jeongyun,Gonzalez-Montiel, Gisela A.,Cheong, Paul Ha-Yeon,Lee, Hong Geun
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supporting information
p. 1096 - 1102
(2021/01/26)
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- Catalytic and Enantioselective Control of the C–N Stereogenic Axis via the Pictet–Spengler Reaction
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An unprecedented example of a chiral phosphoric acid-catalyzed atroposelective Pictet–Spengler reaction of N-arylindoles is reported. Highly enantioenriched N-aryl-tetrahydro-β-carbolines with C?N bond axial chirality are obtained via dynamic kinetic reso
- Kim, Ahreum,Kim, Aram,Park, Sunjung,Kim, Sangji,Jo, Hongil,Ok, Kang Min,Lee, Sang Kook,Song, Jayoung,Kwon, Yongseok
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supporting information
p. 12279 - 12283
(2021/05/03)
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- Gold-catalyzed spirocyclization of furan-ynones and unexpected skeleton rearrangement of the resulting spirohydrofurans
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A gold-catalyzed cyclization of aniline-tethered furan-ynones has been developed. The reaction proceeds via trapping of the resulting stabilized cationic intermediate with an amide group leading to polycycles featured with a spiro-cyclohexadienonehydrofur
- Chen, Yulong,Xu, Wei,Xie, Xin,Pei, Miaomiao,Lu, Mingduo,Wang, Yaotong,Liu, Yuanhong
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supporting information
p. 1090 - 1095
(2021/02/01)
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- One-Pot, Three-Step Synthesis of Benzoxazinones via Use of the Bpin Group as a Masked Nucleophile
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The utilization of the Bpin group as a pronucleophile to facilitate the assembly of cyclic carbamates has been achieved. This one-pot process involves an initial copper-catalyzed borylation, a subsequent C-B bond oxidation to generate the reactive alcohol
- Larin, Egor M.,Torelli, Alexa,Loup, Joachim,Lautens, Mark
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supporting information
p. 2720 - 2725
(2021/04/05)
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- Cycloisomerization of Carbamoyl Chlorides in Hexafluoroisopropanol: Stereoselective Synthesis of Chlorinated Methylene Oxindoles and Quinolinones
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Hexafluoroisopropanol (HFIP) was employed as an additive for the generation of 3-(chloromethylene)oxindoles via the chloroacylation of alkyne-tethered carbamoyl chlorides. This reaction avoids the use of a metal catalyst and accesses products in high yields and stereoselectivities. Additionally, this reaction is scalable and proved amenable to a series of product derivatizations, including the synthesis of nintedanib. The reactivity of alkene-tethered carbamoyl chlorides with hexafluoroisopropanol (HFIP) was harnessed towards the synthesis of 2-quinolinones.
- Bajohr, Jonathan,Lautens, Mark,Mirabi, Bijan,Rodríguez, José F.,Whyte, Andrew,Zhang, Anji
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supporting information
p. 18478 - 18483
(2021/07/19)
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- Bimetallic Bis-NHC-Ir(III) Complex Bearing 2-Arylbenzo[d]oxazolyl Ligand: Synthesis, Catalysis, and Bimetallic Effects
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Herein, an unprecedented bimetallic bis-NHC Cp*Ir complex 1 bearing 2-arylbenzo[d]oxazolyl and NHC ligands is reported. A significant increase in activity was observed for N-methylation of amines and reduction of aldehydes with MeOH catalyzed by 1 compared to the monometallic analogues (2-11). Under the optimal conditions, it showed to be highly effective in N-methylation of nitroarenes with MeOH as both C1 and H2 source. Substrates, including aromatic amines, ketones, and nitro compounds with various functional groups, can be well-tolerated. Mechanistic studies and DFT calculation highlight the significance of bimetallic centers cooperativity.
- Huang, Shuang,Hong, Xi,Cui, He-Zhen,Zhan, Bing,Li, Zhi-Ming,Hou, Xiu-Feng
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p. 3514 - 3523
(2020/10/09)
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- B(C6F5)3-Catalyzed cyclization of alkynes: direct synthesis of 3-silyl heterocyclic compounds
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An efficient one-pot strategy for easy access to 3-silyl heterocyclic compounds was developedviaa B(C6F5)3-catalyzed cycloaddition reaction ofo-(1-alkynyl)(thio)anisoles oro-(1-alkynyl)-N-methylaniline. In this reaction, benzenethiophene, benzofuran or indole skeletons could be constructed by an intermolecular cyclization with diphenylsilane. This protocol elicited moderate-to-good yields with metal-free reaction systems.
- Li, Mengxing,Wang, Ting,An, Zhenyu,Yan, Rulong
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supporting information
p. 11953 - 11956
(2020/10/15)
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- Bifunctional Phosphine Ligand Enabled Gold-Catalyzed Alkynamide Cycloisomerization: Access to Electron-Rich 2-Aminofurans and Their Diels–Alder Adducts
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By using biphenyl-2-ylphosphines functionalized with a remote tertiary amino group as a ligand, readily available acetylenic amides are directly converted into 2-aminofurans devoid of any electron-withdrawing and hence deactivating/stabilizing substituent
- Li, Xingguang,Ma, Xu,Wang, Zhixun,Liu, Pei-Nian,Zhang, Liming
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supporting information
p. 17180 - 17184
(2019/11/03)
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- N -Methylation of ortho -substituted aromatic amines with methanol catalyzed by 2-arylbenzo [d] oxazole NHC-Ir(iii) complexes
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Seven new chelated cyclometalated Ir complexes of ABON,P, ABON,O, and ABON,C(carbene) based on a rigid and tunable 2-arylbenzo[d]oxazole backbone have been prepared for the N-methylation of amines. Among these three coordinated modes, ABON,C(carbene)-chelated iridium-based catalysts exhibited good performance in the monomethylation of aromatic amines with methanol (MeOH) as the green methylation reagent. The steric-modified synthesis of ABON,C(carbene) complexes was described. The most active ABON,C(carbene) complex with marginal steric hindrance as a catalyst was obtained from the benzoxazole ring without a substituent and methyl group of the benzimidazole ring on the N-heterocyclic carbene (NHC) ligand. A variety of amines including para- and meta-substituted aromatic amines, as well as heterocyclic amines, were formulated as suitable substrates. Importantly, this catalyst considerably promoted the yield of the N-methylation of ortho-substituted aromatic amines. Controlled kinetic experiments and deuterium-labeling reactions of these ortho-substituted amines were conducted under optimized conditions. On the basis of the experimental results, a plausible mechanism was proposed.
- Huang, Shuang,Hong, Xi,Cui, He-Zhen,Zhou, Quan,Lin, Yue-Jian,Hou, Xiu-Feng
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p. 5072 - 5082
(2019/04/17)
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- Room temperature N-heterocyclic carbene manganese catalyzed selective N-alkylation of anilines with alcohols
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The first example of room temperature non-noble metal homogeneous system catalyzed selective N-alkylation of anilines with alcohols by a bis-NHC manganese complex is presented. This system was applied to a large range of alcohols and anilines, including biologically relevant motifs and challenging methanol. Experimental and computational studies suggest an outer-sphere mechanism for this NHC-Mn system.
- Huang, Ming,Li, Yukui,Li, Yinwu,Liu, Jiahao,Shu, Siwei,Liu, Yan,Ke, Zhuofeng
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supporting information
p. 6213 - 6216
(2019/06/07)
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- Efficient assembly of ynones via palladium-catalyzed sequential carbonylation/alkynylation
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Based on the intramolecular Heck-type reaction, a convenient and efficient strategy to construct functionalized ynones by a palladium-catalyzed cascade annulation reaction has been developed. This reaction possesses good functional group compatibility, a broad substrate scope, and high atom- and step-economy. Furthermore, this approach could also be extended to direct alkynylation that gave another route to synthesize dihydrobenzofurans.
- Hu, Miao,Gao, Yang,Wu, Wanqing,Li, Jianxiao,Li, Chunsheng,Zhang, Hao,Jiang, Huanfeng
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supporting information
p. 7383 - 7392
(2018/10/24)
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- A catalyst-free and additive-free method for the synthesis of benzothiazolethiones from: O -iodoanilines, DMSO and potassium sulfide
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Under catalyst-free and additive-free conditions, a novel, convenient, eco-friendly method for the synthesis of benzothiazolethiones has been developed. The three-component reaction of o-iodoanilines and K2S with DMSO proceeded smoothly and the corresponding benzothiazolethiones were obtained with good isolated yields. Meanwhile, this method could be used for the synthesis of thioureas from primary diamines. Furthermore, mechanism research showed that DMSO not only functioned as a carbon source, but also as a mild oxidant in this reaction.
- Zhu, Xiaoming,Li, Wenguang,Luo, Xiai,Deng, Guobo,Liang, Yun,Liu, Jianbing
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supporting information
p. 1970 - 1974
(2018/05/23)
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- Cp?Rh(iii) catalyzed: Ortho -halogenation of N -nitrosoanilines by solvent-controlled regioselective C-H functionalization
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We present a novel, efficient, and regioselective method for the rhodium-catalyzed direct C-H ortho-halogenation of anilines that involves a removable N-nitroso directing group. This method featured mild reaction conditions, wide substrate scope, good functional group tolerance and satisfactory yields. To maintain the high ortho-regioselectivity and conversion, increasing the steric hindrance of the solvent was critical. Preliminary mechanistic studies suggest that C-H activation may be involved in the rate-determining step.
- Peng, Qiujun,Hu, Jian,Huo, Jiyou,Yuan, Hongshun,Xu, Lanting,Pan, Xianhua
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supporting information
p. 4471 - 4481
(2018/06/29)
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- BIARYL DERIVATIVE AS GPR120 AGONIST
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The present invention relates to a biaryl derivative expressed by the chemical formula 1, a method for producing the biaryl derivative, a pharmaceutical composition comprising same, and use of same, the biaryl derivative expressed by the chemical formula 1, as a GPR120 agonist, promoting GLP-1 generation in the gastro-intestinal tract, reducing insulin resistance in the liver, muscles and the like from anti-inflammatory activity in the macrophage, pancreatic cells and the like, and allowing effective use in prevention or treatment of inflammation or metabolic diseases such as diabetes, complications from diabetes, obesity, non-alcoholic fatty liver disease, fatty liver disease, and osteoporosis.
- -
-
Paragraph 0402; 0403
(2017/11/17)
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- Transition-Metal-Free Amination of Pyridine-2-sulfonyl Chloride and Related N-Heterocycles Using Magnesium Amides
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A new transition-metal-free amination of pyridine-2-sulfonyl chloride and related N-heterocycles using magnesium amides of type R2NMgCl·LiCl is reported. Additionally, the directed ortho-magnesiation of pyridine-2-sulfonamides using TMPMgCl·LiCl was investigated. Reaction of the magnesium intermediates with various electrophiles and subsequent amination using magnesium amides led to a range of 2,3-functionalized pyridines. Also, cyclization reactions providing an aza-indole and an aza-carbazole were carried out.
- Balkenhohl, Moritz,Fran?ois, Cyril,Sustac Roman, Daniela,Quinio, Pauline,Knochel, Paul
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supporting information
p. 536 - 539
(2017/02/10)
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- Stereoselective Synthesis of Methylene Oxindoles via Palladium(II)-Catalyzed Intramolecular Cross-Coupling of Carbamoyl Chlorides
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We report a highly robust, general and stereoselective method for the synthesis of 3-(chloromethylene)oxindoles from alkyne-tethered carbamoyl chlorides using PdCl2(PhCN)2 as the catalyst. The transformation involves a stereo- and regioselective chloropalladation of an internal alkyne to generate a nucleophilic vinyl PdII species, which then undergoes an intramolecular cross-coupling with a carbamoyl chloride. The reaction proceeds under mild conditions, is insensitive to the presence of moisture and air, and is readily scalable. The products obtained from this reaction are formed with >95:5 Z:E selectivity in nearly all cases and can be used to access biologically relevant oxindole cores. Through combined experimental and computational studies, we provide insight into stereo- and regioselectivity of the chloropalladation step, as well as the mechanism for the C-C bond forming process. Calculations provide support for a mechanism involving oxidative addition into the carbamoyl chloride bond to generate a high valent PdIV species, which then undergoes facile C-C reductive elimination to form the final product. Overall, the transformation constitutes a formal PdII-catalyzed intramolecular alkyne chlorocarbamoylation reaction.
- Le, Christine M.,Sperger, Theresa,Fu, Rui,Hou, Xiao,Lim, Yong Hwan,Schoenebeck, Franziska,Lautens, Mark
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supporting information
p. 14441 - 14448
(2016/11/13)
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- A Palladium-Catalyzed Double Carbonylation Approach to Isatins from 2-Iodoanilines
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A high-yielding procedure for the synthesis of isatins has been developed. Sequential Pd-catalyzed double carbonylation of 2-iodoanilines with near stoichiometric amounts of CO followed by acid-promoted cyclization readily affords an array of isatins. The conversion of 2-iodoanilines to isatins in good to excellent yields was found to proceed with good functional group tolerance. This protocol proved adaptable to 13C-isotope labeling of isatins, which was extended to the synthesis of the 13C-isotope labeled antiviral drug metisazone and the experimental anti-schizophrenia drug ML137.
- Laursen, Simon R.,Jensen, Mikkel T.,Lindhardt, Anders T.,Jacobsen, Mikkel F.,Skrydstrup, Troels
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supporting information
p. 1881 - 1885
(2016/05/09)
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- Radical Hydrodeiodination of Aryl, Alkenyl, Alkynyl, and Alkyl Iodides with an Alcoholate as Organic Chain Reductant through Electron Catalysis
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A simple and efficient method for radical hydrodeiodination is reported. The novel approach uses electron catalysis. In situ generated Na-alcoholates are introduced as radical chain reducing reagents and reactions work with O2as cheap initiator. Hydrodeiodination works on aryl, alkenyl, alkynyl iodides and a tert-alkyl iodide also gets reduced applying the method. Albeit less general, the method is also applicable to the reduction of aryl bromides. The novel reagent is successfully used to conduct typical reductive radical cyclization reactions and mechanistic studies are reported.
- Dewanji, Abhishek,Mück-Lichtenfeld, Christian,Studer, Armido
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supporting information
p. 6749 - 6752
(2016/06/09)
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- A new synthesis of indoles via intramolecular cyclization of ?-alkynyl N,N-dialkylanilines promoted by KOt-Bu/DMSO
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2-Aryl indoles could be prepared in excellent yields via the intramolecular cyclization of ?-alkynyl N,N-dialkylanilines. The reaction is efficiently promoted by the catalytic amount of KOt-Bu in DMSO at room temperature. A reaction mechanism involving α-
- Chen, Yan-Yan,Chen, Jia-Hua,Zhang, Niu-Niu,Ye, Lin-Miao,Zhang, Xue-Jing,Yan, Ming
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supporting information
p. 478 - 481
(2015/03/05)
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- A new synthesis of indoles via intramolecular cyclization of ο-alkynyl N,N-dialkylanilines promoted by KOt-Bu/DMSO
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2-Aryl indoles could be prepared in excellent yields via the intramolecular cyclization of ο-alkynyl N,N-dialkylanilines. The reaction is efficiently promoted by the catalytic amount of KOt-Bu in DMSO at room temperature. A reaction mechanism involving α-
- Chen, Yan-Yan,Chen, Jia-Hua,Zhang, Niu-Niu,Ye, Lin-Miao,Zhang, Xue-Jing,Yan, Ming
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supporting information
p. 478 - 481
(2015/04/27)
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- An Exclusively trans-Selective Chlorocarbamoylation of Alkynes Enabled by a Palladium/Phosphaadamantane Catalyst
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Pharmaceutically relevant methylene oxindoles are synthesized by a palladium(0)-catalyzed intramolecular chlorocarbamoylation reaction of alkynes. A relatively underexplored class of caged phosphine ligands is uniquely suited for this transformation, enab
- Le, Christine M.,Hou, Xiao,Sperger, Theresa,Schoenebeck, Franziska,Lautens, Mark
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supporting information
p. 15897 - 15900
(2016/01/28)
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- An efficient approach to 1,2,3-trisubstituted indole via rhodium catalyzed carbene Csp3-H bond insertion
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A method for convenient synthesis of N-alkyl-2-aryl-indole-3-carbaldehyde has been described. A variety of highly valuable indolyl aldehydes have been prepared through this method. Electron donating groups on both aromatic rings (anilinyl and benzyl) facilitate the formation of the desired products. A benzylic C-H insertion by rhodium carbene is the key step for this transformation. This journal is
- Shen, Mei-Hua,Pan, Ying-Peng,Jia, Zhi-Hong,Ren, Xin-Tao,Zhang, Ping,Xu, Hua-Dong
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supporting information
p. 4851 - 4854
(2015/05/05)
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- Expanded-ring N-heterocyclic carbenes efficiently stabilize gold(I) cations, leading to high activity in π-acid-catalyzed cyclizations
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A series of six- and seven-membered expanded-ring N-heterocyclic carbene (er-NHC) gold(I) complexes has been synthesized using different synthetic approaches. Complexes with weakly coordinating anions [(er-NHC)AuX] (X -=BF4-, NTf2-, OTf -) were generated in solution. According to their 13C NMR spectra, the ionic character of the complexes increases in the order X -=Cl-2--4-. Additional factors for stabilization of the cationic complexes are expansion of the NHC ring and the attachment of bulky substituents at the nitrogen atoms. These er-NHCs are bulkier ligands and stronger electron donors than conventional NHCs as well as phosphines and sulfides and provide more stabilization of [(L)Au+] cations. A comparative study has been carried out of the catalytic activities of five-, six-, and seven-membered carbene complexes [(NHC)AuX], [(Ph3P)AuX], [(Me2S)AuX], and inorganic compounds of gold in model reactions of indole and benzofuran synthesis. It was found that increased ionic character of the complexes was correlated with increased catalytic activity in the cyclization reactions. As a result, we developed an unprecedentedly active monoligand cationic [(THD-Dipp)Au]BF4 (1,3-bis(2,6-diisopropylphenyl) -3,4,5,6-tetrahydrodiazepin-2-ylidene gold(I) tetrafluoroborate) catalyst bearing seven-membered-ring carbene and bulky Dipp substituents. Quantitative yields of cyclized products were attained in several minutes at room temperature at 1 mol% catalyst loadings. The experimental observations were rationalized and fully supported by DFT calculations. What a difference a ring makes: Expanded-ring N-heterocyclic carbenes (er-NHC) surpass their five-membered ring counterparts, as well as Ph3P and Me2S, in the stabilization of cationic gold(I) species due to increased steric protection and electron-donating properties. A monoligand cationic [(THD-Dipp)Au]BF 4 (Dipp=2,6-diisopropylphenyl) complex bearing a seven-membered ring carbene and bulky Dipp substituents exhibits unprecedentedly high catalytic activity in indole and benzofuran synthesis (see scheme).
- Morozov, Oleg S.,Lunchev, Andrey V.,Bush, Alexander A.,Tukov, Aleksandr A.,Asachenko, Andrey F.,Khrustalev, Victor N.,Zalesskiy, Sergey S.,Ananikov, Valentine P.,Nechaev, Mikhail S.
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supporting information
p. 6162 - 6170
(2014/05/20)
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- Intramolecular cyclization of alkynyl α-ketoanilide utilizing [1,2]-phospha-brook rearrangement catalyzed by phosphazene base
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A novel catalytic cyclization reaction of alkynyl α-ketoanilide was developed by utilizing the [1,2]-phospha-Brook rearrangement. This reaction involves the generation of an amide enolate via the umpolung process, that is the addition of dialkyl phosphite to a keto moiety followed by the [1,2]-phospha-Brook rearrangement, and the subsequent intramolecular addition of the enolate to an alkyne to afford 3,4-dihydro-2-quinolone derivatives. Under high-temperature reaction conditions, further rearrangement of the allylic phosphate moiety occurs to provide 2-quinolone derivatives.
- Kondoh, Azusa,Aoki, Takuma,Terada, Masahiro
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supporting information
p. 3528 - 3531
(2014/07/21)
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- CuBr-promoted tandem cyclization/trifluoromethylation of 2-alkynylanilines: Efficient synthesis of 3-trifluoromethylindoles
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A new efficient strategy for the synthesis of 3-trifluoromethyl-indoles was developed through tandem cyclization/ trifluoromethylation of 2-alkynylanilines and Umemoto’s reagent under effect of CuBr. The reaction features the use of cheap copper salt, mil
- Ge, Guangcun,Huang, Xiaojun,Ding, Changhua,Li, Hao,Wan, Shili,Hou, Xuelong
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supporting information
p. 727 - 733
(2014/10/16)
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- Room-temperature palladium-catalyzed intramolecular oxidative aminocarbonylation of vinylic C(sp2)-H bonds with amines and CO
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A new, mild route to access 3-methyleneindolin-2-ones is presented that proceeds through a room-temperature, palladium-catalyzed intramolecular oxidative aminocarbonylation of alkenes with amines and CO. This method represents a new aminocarbonylation str
- Yang, Xu-Heng,Li, Kai,Song, Ren-Jie,Li, Jin-Heng
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supporting information
p. 616 - 623
(2014/02/14)
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- Room-Temperature Palladium-Catalyzed Intramolecular Oxidative Aminocarbonylation of Vinylic C(sp2)-H Bonds with Amines and CO
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A new, mild route to access 3-methyleneindolin-2-ones is presented that proceeds through a room-temperature, palladium-catalyzed intramolecular oxidative aminocarbonylation of alkenes with amines and CO. This method represents a new aminocarbonylation str
- Yang, Xu-Heng,Li, Kai,Song, Ren-Jie,Li, Jin-Heng
-
supporting information
p. 616 - 623
(2015/10/05)
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- A High-Throughput Assay for Arylamine Halogenation Based on a Peroxidase-Mediated Quinone-Amine Coupling with Applications in the Screening of Enzymatic Halogenations
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Arylhalides are important building blocks in many fine chemicals, pharmaceuticals and agrochemicals, and there has been increasing interest in the development of more "green" halogenation methods based on enzyme catalysis. However, the screening and development of new enzymes for biohalogenation has been hampered by a lack of high-throughput screening methods. Described herein is the development of a colorimetric assay for detecting both chemical and enzymatic arylamine halogenation reactions in an aqueous environment. The assay is based on the unique UV/Vis spectrum created by the formation of an ortho-benzoquinone-amine adduct, which is produced by the peroxidase-catalysed benzoquinone generation, followed by Michael addition of either a halogenated or non-halogenated arylamine. This assay is sensitive, rapid and amenable to high-throughput screening platforms. We have also shown this assay to be easily coupled to a flavin-dependent halogenase, which currently lacks any convenient colorimetric assay, in a "one-pot" workflow.
- Hosford, Joseph,Shepherd, Sarah A.,Micklefield, Jason,Wong, Lu Shin
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supporting information
p. 16759 - 16763
(2016/02/12)
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- Remarkable switch in the regiochemistry of the iodination of anilines by N-iodosuccinimide: Synthesis of 1,2-dichloro-3,4-diiodobenzene
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Direct iodination of anilines by NIS in polar solvents (such as DMSO) affords p-iodinated products with up to >99% regioselectivity. Switching to less polar solvents (such as benzene) in the presence of AcOH inverts this outcome toward dramatically increased or preferential generation of the o-isomers, also with up to >99% regioselectivity. This finding was exploited in the synthesis of 1,2-dichloro-3,4-diiodobenzene. Georg Thieme Verlag Stuttgart - New York.
- Shen, Hao,Vollhardt, K. Peter C.
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supporting information; experimental part
p. 208 - 214
(2012/03/11)
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- A CuAAC/Ullmann C-C coupling tandem reaction: Copper-catalyzed reactions of organic azides with N -(2-Iodoaryl)propiolamides or 2-iodo- N -(prop-2-ynyl)benzenamines
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A novel copper-catalyzed tandem reaction was developed by utilizing two famous copper-catalyzed reactions, CuAAC and Ullmann coupling. The trapping of the C-Cu intermediate produced in CuAAC led to further formation of an aryl C-C bond through intramolecu
- Cai, Qian,Yan, Jiajie,Ding, Ke
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supporting information; experimental part
p. 3332 - 3335
(2012/08/28)
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- Palladium-catalyzed coupling of ortho-alkynylanilines with terminal alkynes under aerobic conditions: Efficient synthesis of 2,3-disubstituted 3-alkynylindoles
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Two nucleophiles, one triple bond: Under aerobic conditions, palladium-catalyzed direct coupling of o-alkynylanilines and terminal alkynes took place smoothly to afford the 2,3-disubstituted 3-alkynylindoles 3 in good to excellent yields. The intermediate A was characterized and a retro-aminopalladation of B was observed for the first time. Copyright
- Yao, Bo,Wang, Qian,Zhu, Jieping
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supporting information
p. 12311 - 12315
(2013/02/23)
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- Platinum-catalyzed consecutive C-N bond formation-[1,3] shift of carbamoyl and ester groups
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The reaction of ortho-alkynylphenylureas 1 having a carbamoyl group attached to the nitrogen atom proceeded in the presence of catalytic amounts of PtI4, affording corresponding indole-3-carbamides 2 in moderate to high yields. In addition, the platinum-catalyzed cyclization of ortho-alkynylphenyl carbamates 3 afforded corresponding indole-3-carboxylates 4 in good yields. The present reaction proceeds through the intramolecular addition of carbon-nitrogen bonds to triple bonds, the so-called carboamination.
- Nakamura, Itaru,Sato, Yusuke,Konta, Sayaka,Terada, Masahiro
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supporting information; experimental part
p. 2075 - 2077
(2009/09/05)
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- Samarium(II)-mediated spirocyclization by intramolecular aryl radical addition onto an aromatic ring
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(Chemical Equation Presented) Samarium(II)-mediated spirocyclization by intramolecular addition of aryl radicals onto an aromatic ring was achieved by the reaction of N-(2-iodophenyl)-N-alkylbenzamides with SmI2 in the presence of HMPA, yielding spirocyclic indolin-2-one derivatives. The ether congeners afford spirocyclic benzofuran derivatives in moderate yields by aryl radical addition onto a benzene ring without having an electron-withdrawing group. The reaction with other aryl groups such as naphthalene and indole rings is also described.
- Iwasaki, Hiroki,Eguchi, Toru,Tsutsui, Nozomi,Ohno, Hiroaki,Tanaka, Tetsuaki
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supporting information; scheme or table
p. 7145 - 7152
(2009/05/07)
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- Gold- and indium-catalyzed synthesis of 3- and 6-sulfonylindoles from ortho-alkynyl-N-sulfonylanilines
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(Chemical Equation Presented) Consecutive formation of C-N and C-S bonds: The gold-catalyzed intramolecular aminosulfonylation of 2-alkynyl-N- sulfonylanilines 1 (R1 = H) produces 3-sulfonylindoles 2 in good to high yields, whereas the indium-c
- Nakamura, Itaru,Yamagishi, Uichiro,Song, Dschun,Konta, Sayaka,Yamamoto, Yoshinori
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p. 2284 - 2287
(2008/02/12)
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- Highly specific N-monomethylation of primary aromatic amines
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A synthetic methodology for the specific conversion of primary aromatic amines into their N-monomethyl derivatives under very mild conditions is presented. Anilines are treated with 4-nitrobenzenesulfonyl (nosyl) chloride to generate the corresponding sulfonamides 2 in high yields. The subsequent N-methylation reaction of the sulfonamides 2 with a solution of diazomethane is rapid and quantitative. Removal of the nosyl protecting group is readily carried out using the reagent system mercaptoacetic acid/1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) affording the N-monomethylated aromatic amines 4. The procedure is convenient, efficient, and gives rise to the N-monomethyl-anilines exclusively.
- Le Pera, Adolfo,Leggio, Antonella,Liguori, Angelo
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p. 6100 - 6106
(2007/10/03)
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- Palladium-catalysed intramolecular annulation of 2-haloanilines and ketones: Enolate arylation vs. nucleophilic addition to the carbonyl group
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Two alternative annulation pathways involving either the enolate arylation or the addition to the ketone carbonyl group can operate in the Pd-catalysed intramolecular coupling of 2-haloanilines and ketones.
- Sole,Vallverdu,Peidro,Bonjoch
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p. 1888 - 1889
(2007/10/03)
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- Synthesis of 2,3-disubstituted indoles via palladium-catalyzed annulation of internal alkynes
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The palladium-catalyzed coupling of 2-iodoaniline and the corresponding N-methyl, -acetyl, and -tosyl derivatives with a wide variety of internal alkynes provides 2,3-disubstituted indoles in good-to-excellent yields. The best results are obtained by empl
- Larock,Yum,Refvik
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p. 7652 - 7662
(2007/10/03)
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- 2-amino-4H-3,1-benzoxazin-4-ones as inhibitors of C1r serine protease
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A series of 2-amino-4H-3,1-benzoxazin-4-ones have been synthesized and evaluated as inhibitors of the complement enzyme C1r. C1r is a serine protease at the beginning of the complement cascade, and complement activation by β-amyloid may represent a major contributing pathway to the neuropathology of Alzheimer's disease. Compounds such as 7-chloro-2-[(2- iodophenyl)amino]benz[d][1,3]oxazin-4-one (32) and 7-methyl-2-[(2- iodophenyl)amino]benz[d][1,3]oxazin-4-one (37) show improved potency compared to the reference compound FUT-175. Many of these active compounds also possess increased selectivity for C1r compared to trypsin and enhanced hydrolytic stability relative to 2-(2-iodophenyl)-4H-3,1-benzoxazin-4-one (1).
- Hays, Sheryl J.,Caprathe, Bradley W.,Gilmore, John L.,Amin, Nilam,Emmerling, Mark R.,Michael, Walter,Nadimpalli, Ravi,Nath, Rathna,Raser, Kadee J.,Stafford, Daniel,Watson, Desiree,Wang, Kevin,Jaen, Juan C.
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p. 1060 - 1067
(2007/10/03)
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- 2-SUBSTITUTED-4H-3, 1-BENZOXAZIN-4-ONES AND BENZTHIAZIN-4-ONES AS INHIBITORS OF COMPLEMENT C1R PROTEASE FOR THE TREATMENT OF INFLAMMATORY PROCESSES
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This invention concerns certain 2-substituted-3,1-benzoxazin-4-ones and benzthiazinones as complement Clr protease inhibitors and antiinflammatory agents, pharmaceutical compositions containing them, methods of using them, and processes for their preparat
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- A NEW SYNTHESIS OF 3-SUBSTITUTED INDOLINES AND INDOLES
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3-Phenyl- and 3-alkyl-3-hydroxyindolines were synthesized by intramolecular Barbier reaction of phenyl and alkyl N-(2-iodophenyl)-N-methylaminomethyl ketones with n-BuLi, which were easily prepared from N-methyl-2-iodoaniline and bromomethyl ketones.The treatment of the indolines with acid gave the corresponding indoles in quantitative yields.
- Kihara, Masaru,Iwai, Yasumasa,Nagao, Yoshimitsu
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p. 2279 - 2288
(2007/10/03)
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- Mercury in Organic Chemistry. 26. Synthesis of Heterocycles via Intramolecular Solvomercuration of Aryl Acetylenes
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A number of ortho substituted aryl acetylenes, o-CH3XC6H4YCCR (X=O, S, CO2; Y=-, CO), have been observed to undergo facile intramolecular solvomercuration with mercuric acetate in acetic acid to afford the corresponding benzofuran, benzothiophene, isocoumarin, and chromone organomercuric chlorides, after aqueous sodium chloride workup.The aryl acetylenes m-XC6H4YCH2CCR (X=H, Y=O, R=CH3; X=CH3O, Y=CH2, R=n-C3H7) undergo similar cyclizations to yield mercurated 2H-1-benzopyrans and 1,2-dihydronaphthalenes.The mercuration and subsequent carbonylation of o-R1OC6H4CCR2 1=Si(t-Bu)Me2, R2=CH3; R1=CH3, R2=o-C6H4OCH3> has provided a new approach to the coumarin and coumestan ring systems.
- Larock, Richard C.,Harrison, L. Wayne
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p. 4218 - 4227
(2007/10/02)
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