- Electrophilic fluorination in the synthesis of new fluoroindoles
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Fluorination of trialkylstannylindoles with caesium fluoroxysulfate on Selectfluor(TM) was investigated for the synthesis of inter-alia 2- and 3- fluoroindoles. Caesium fluoroxysulfate gave good yields of these potentially useful intermediates. Selectfluo
- Hodson, Harold F.,Madge, David J.,Slawin, Alexandra N. Z.,Widdowson, David A.,Williams, David J.
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- Diels-Alder reactions of N-tosylpirroles developed in protic ionic liquids. Theoretical studies using DFT methods
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N-Tosyl-2-nitropirrole and N-tosyl-3-nitropirrole react with poorly and activated dienes using protic ionic liquids as reaction media. They exhibit a dienophile character producing the corresponding indoles through a Diels-Alder process. In all cases the
- Rosa, Claudia Della,Ormachea, Carla,Kneeteman, Maria N.,Adam, Claudia,Mancini, Pedro M.E.
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- Silaphenylmercuric triflate catalyzed reactions: Synthesis of a solid-supported mercuric salt catalyst
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Let it flow, let it flow: A procedure to generate the first solid-supported mercuric salt, silaphenylmercuric triflate, is described. Silaphenylmercuric triflate showed remarkable catalytic activity for an indole synthesis, furanoyne cyclization, arylyne
- Yamamoto, Hirofumi,Sasaki, Ikuo,Hirai, Yuki,Namba, Kosuke,Imagawa, Hiroshi,Nishizawa, Mugio
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- A class of indole derivatives and preparation methods and uses thereof
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The present invention relates to the field of medicinal chemistry, discloses a class of indole derivatives and preparation methods and uses thereof. The present invention also discloses a compound comprising the indole structure or a pharmaceutically acce
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Paragraph 0032; 0034-0036; 0086; 0088-0089
(2022/01/12)
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- Synthesis of Azepino[1,2-a]indole-10-amines via [6+1] Annulation of Ynenitriles with Reformatsky Reagent
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Lewis acid-catalyzed [6+1] annulation reactions of 2-cyano-1-propargyl- and 2-alkynyl-1-cyanomethyl-indoles with Reformatsky reagent are described. 8-Aryl, 8-alkyl-, 8-hetaryl-, 9-aryl, and 9-alkyl-azepino[1,2-a]indole amines were obtained through a 7-endo-mode cyclization of the β-aminoacrylate intermediates. The antiproliferative activity of the azepino[1,2-a]indoles analogs against the HCT-116 cells were also examined.
- Iioka, Ryoya,Yorozu, Kohei,Sakai, Yoko,Kawai, Rika,Hatae, Noriyuki,Takashima, Katsuki,Tanabe, Genzoh,Wasada, Hiroaki,Yoshimatsu, Mitsuhiro
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supporting information
p. 1553 - 1558
(2021/02/26)
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- A Series of 2-((1-Phenyl-1H-imidazol-5-yl)methyl)-1H-indoles as Indoleamine 2,3-Dioxygenase 1 (IDO1) Inhibitors
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Indoleamine 2,3-dioxygenase 1 (IDO1) is a promising therapeutic target in cancer immunotherapy and neurological disease. Thus, searching for highly active inhibitors for use in human cancers is now a focus of widespread research and development efforts. I
- Zheng, Yong,Stafford, Paul M.,Stover, Kurt R.,Mohan, Darapaneni Chandra,Gupta, Mayuri,Keske, Eric C.,Schiavini, Paolo,Villar, Laura,Wu, Fan,Kreft, Alexander,Thomas, Kiersten,Raaphorst, Elana,Pasangulapati, Jagadeesh P.,Alla, Siva R.,Sharma, Simmi,Mittapalli, Ramana R.,Sagamanova, Irina,Johnson, Shea L.,Reed, Mark A.,Weaver, Donald F.
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supporting information
p. 2195 - 2205
(2021/05/31)
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- Ester-substituted indoline and preparation method thereof
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The invention provides ester-substituted indoline and a preparation method thereof. The ester-substituted indoline is an indoline compound substituted by different ester groups. Indole is prepared into an epoxy dihydroindole compound, so that the activity
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Paragraph 0016-0018
(2021/01/21)
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- Design, Synthesis, and Antifungal Evaluation of Cryptolepine Derivatives against Phytopathogenic Fungi
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Inspired by the widely antiphytopathogenic application of diversified derivatives from natural sources, cryptolepine and its derivatives were subsequently designed, synthesized, and evaluated for their antifungal activities against four agriculturally important fungi Rhizoctonia solani, Botrytis cinerea, Fusarium graminearum, and Sclerotinia sclerotiorum. The results obtained from in vitro assay indicated that compounds a1-a24 showed great fungicidal property against B. cinerea (EC50 4 μg/mL); especially, a3 presented significantly prominent inhibitory activity with an EC50 of 0.027 μg/mL. In the pursuit of further expanding the antifungal spectrum of cryptolepine, ring-opened compound f1 produced better activity with an EC50 of 3.632 μg/mL against R. solani and an EC50 of 5.599 μg/mL against F. graminearum. Furthermore, a3 was selected to be a candidate to investigate its preliminary antifungal mechanism to B. cinerea, revealing that not only spore germination was effectively inhibited and the normal physiological structure of mycelium was severely undermined but also detrimental reactive oxygen was obviously accumulated and the normal function of the nucleus was fairly disordered. Besides, in vivo curative experiment against B. cinerea found that the therapeutic action of a3 was comparable to that of the positive control azoxystrobin. These results suggested that compound a3 could be regarded as a novel and promising agent against B. cinerea for its valuable potency.
- Chen, Yong-Jia,Liu, Hua,Zhang, Shao-Yong,Li, Hu,Ma, Kun-Yuan,Liu, Ying-Qian,Yin, Xiao-Dan,Zhou, Rui,Yan, Yin-Fang,Wang, Ren-Xuan,He, Ying-Hui,Chu, Qing-Ru,Tang, Chen
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p. 1259 - 1271
(2021/02/16)
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- A facile and versatile electro-reductive system for hydrodefunctionalization under ambient conditions
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A general electrochemical system for reductive hydrodefunctionalization is described, employing the inexpensive and easily available triethylamine (Et3N) as a sacrificial reductant. This protocol is characterized by facile operation, sustainable conditions, and exceptionally wide substrate scope covering the cleavage of C-halogen, N-S, N-C, O-S, O-C, C-C and C-N bonds. Notably, the selectivity and capability of reduction can be conveniently switched by simple incorporation or removal of an alcohol as a co-solvent.
- Huang, Binbin,Guo, Lin,Xia, Wujiong
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supporting information
p. 2095 - 2103
(2021/03/26)
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- Construction of Oxepino[3,2-b]indoles via [4+3] Annulation of 2-Ylideneoxindoles with Crotonate-Derived Sulfur Ylides
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A [4+3] annulation of 2-ylideneoxindoles with crotonate-derived sulfur ylides has been developed. A series of oxepino[3,2-b]indoles were prepared in moderate to excellent yields (62-93%) under mild conditions. Moreover, the synthetic oxepino[3,2-b] indoles can be further transformed into more complex cyclopropa[5,6]oxepino[3,2-b]indoles via a [2+1] cyclopropanation. In addition, the synthetic compounds show certain antiproliferative activity against K562 and MCF-7 cells, and its IC50 values for these two kinds of tumor cells up to 5.40±0.88 μM and 18.41±0.50 μM, respectively. (Figure presented.).
- Fei, Xing-Hai,Guan, Xiang,He, Bin,Li, Zong-Qin,Wang, Da-Peng,Yang, Fen-Fen,Yang, Yuan-Yong,Zhao, Yong-Long,Zhou, Meng
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supporting information
p. 3018 - 3024
(2021/06/26)
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- A Catalytic Construction of Indoles via Formation of Ruthenium Vinylidene Species from N-Arylynamides
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Treatment of ynamides with a catalytic amount of TpRuCl(PPh3)2 resulted in the construction of indole scaffolds known as privileged structure motifs. This reaction involved a cascade of 1,2-rearrangement and cyclization carrying out C?C bond formation via a ruthenium vinylidene intermediate, as revealed by a deuterium-labeling experiments. Furthermore, the transformation of multi-functionalized ynamide, derived from a practical drug molecule, showed a high functional group tolerance of this reaction. (Figure presented.).
- Tayu, Masanori,Watanabe, Ryuta,Isogi, Satoshi,Saito, Nozomi
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supporting information
p. 1147 - 1151
(2021/01/04)
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- Iodine-Mediated Electrochemical C(sp2)-H Amination: Switchable Synthesis of Indolines and Indoles
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A metal-free electrochemical intramolecular C(sp2)-H amination using iodine as a mediator was developed. This method enables a switchable synthesis of indoline and indole derivatives, respectively, from easily available 2-vinyl anilines.
- Hu, Kangfei,Zhang, Yan,Zhou, Zhenghong,Yang, Yu,Zha, Zhenggen,Wang, Zhiyong
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supporting information
p. 5773 - 5777
(2020/08/05)
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- Transition-Metal-Free and Visible-Light-Mediated Desulfonylation and Dehalogenation Reactions: Hantzsch Ester Anion as Electron and Hydrogen Atom Donor
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Novel approaches for N- and O-desulfonylation under room temperature (rt) and transition-metal-free conditions have been developed. The first methodology involves the transformation of a variety of N-sulfonyl heterocycles and phenyl benzenesulfonates to the corresponding desulfonylated products in good to excellent yields using only KOtBu in dimethyl sulfoxide (DMSO) at rt. Alternately, a visible light method has been used for deprotection of N-methyl-N-arylsulfonamides with Hantzsch ester (HE) anion serving as the visible-light-absorbing reagent and electron and hydrogen atom donor to promote the desulfonylation reaction. The HE anion can be easily prepared in situ by reaction of the corresponding HE with KOtBu in DMSO at rt. Both protocols were further explored in terms of synthetic scope as well as mechanistic aspects to rationalize key features of desulfonylation processes. Furthermore, the HE anion induces reductive dehalogenation reaction of aryl halides under visible light irradiation.
- Heredia, Micaela D.,Guerra, Walter D.,Barolo, Silvia M.,Fornasier, Santiago J.,Rossi, Roberto A.,Budén, Mariá E.
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supporting information
p. 13481 - 13494
(2020/12/15)
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- Electron Transfer Photoredox Catalysis: Development of a Photoactivated Reductive Desulfonylation of an Aza-Heteroaromatic Ring
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Herein, we report a protocol for desulfonylation of aza-heteroaromatic rings via photoinduced electron transfer and hydrogen atom transfer. This general protocol has a wide substrate range and moderate to good yields. The utility of the method was demonstrated by the chemoselective desulfonylation of a molecule containing both an aliphatic and an aromatic sulfonamide. (Figure presented.).
- Qiang-Liu,Liu, Yu-Xiu,Song, Hong-Jian,Wang, Qing-Min
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supporting information
p. 3110 - 3115
(2020/07/04)
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- Rhodium-Catalyzed Intermolecular Cyclopropanation of Benzofurans, Indoles, and Alkenes via Cyclopropene Ring Opening
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The generation of metal carbenoids via ring opening of cyclopropenes by transition metals offers a simple entry into highly reactive intermediates. Herein, we describe a diastereoselective intermolecular rhodium-catalyzed cyclopropanation of heterocycles and alkenes using cyclopropenes as carbene precursors with a low loading of a commercially available rhodium catalyst. The reported method is scalable and could be performed with catalyst loadings as low as 0.2 mol %, with no impact to the reaction yield or selectivity.
- Jeyaseelan, Rubaishan,Lautens, Mark,Ross, Rachel J.
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supporting information
(2020/06/29)
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- A NaH-promoted N-detosylation reaction of diverse p-toluenesulfonamides
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A NaH-mediated detosylation reaction of various Ts-protected indoles, azaheterocycles, anilines and dibenzylamine was reported. The method features cheap reagent, convenient operations, mild reaction conditions and broad substrate scope. Moreover, this study revealed that the loading of NaH in tosylation reactions of nitrogen-containing compounds with NaH as a base in DMA or DMF should be controlled due to the possibility of adverse detosylation.
- Sun, Wanwan,Chen, Xiaobei,Hu, Ying,Geng, Huihui,Jiang, Yuanrui,Zhou, Yuxin,Zhu, Wenjing,Hu, Min,Hu, Haohua,Wang, Xingyi,Wang, Xinli,Zhang, Shilei,Hu, Yanwei
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supporting information
(2020/10/05)
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- Application of A-ring modified cryptoxine derivative in prevention and treatment of agricultural plant diseases
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The invention discloses application of any compound of A-ring modified cryptolepine derivatives L-1 to L-10 in prevention and treatment of agricultural plant diseases. Activity test results show thatthe compound has potential inhibitory activity on four p
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Paragraph 0013; 0015
(2020/12/31)
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- B(C6F5)3-Catalyzed Highly Chemoselective Reduction of Isatins: Synthesis of Indolin-3-ones and Indolines
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A chemo- and site-selective reduction reaction of isatin derivatives using catalyst B(C6F5)3 and hydrosilanes is described. This transformation is operationally simple, proceeds under mild conditions, and is resistant to various functional groups. Thus, this efficient reaction using a combination of B(C6F5)3 and BnMe2SiH or B(C6F5)3 and Et2SiH2 could potentially be utilized to produce various indolin-3-ones and indolines, without the need for multistep procedures and metal catalysis conditions.
- Jeong, Hyojin,Han, Nara,Hwang, Dong Wook,Ko, Haye Min
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p. 8150 - 8155
(2020/11/02)
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- Ir-Catalyzed Reversible Acceptorless Dehydrogenation/Hydrogenation of N-Substituted and Unsubstituted Heterocycles Enabled by a Polymer-Cross-Linking Bisphosphine
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The polystyrene-cross-linking bisphosphine ligand PS-DPPBz was effective for the Ir-catalyzed reversible acceptorless dehydrogenation/hydrogenation of N-heterocycles. Notably, this protocol is applicable to the dehydrogenation of N-substituted indoline derivatives with various N-substituents with different electronic and steric natures. A reaction pathway involving oxidative addition of an N-adjacent C(sp3)-H bond to a bisphosphine-coordinated Ir(I) center is proposed for the dehydrogenation of N-substituted substrates.
- Zhang, Deliang,Iwai, Tomohiro,Sawamura, Masaya
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supporting information
p. 5240 - 5245
(2020/07/03)
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- Nortopsentin alkaloid derivatives and preparation thereof, and application of nortopsentin alkaloid derivatives to prevention and treatment of diseases and insect pests
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The invention relates to nortopsentin alkaloid derivatives I and preparation thereof, and application of the nortopsentin alkaloid derivatives I to resisting of plant viruses and pathogens and killingof insects. The nortopsentin alkaloid derivatives I in
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Paragraph 0034-0035; 0038
(2019/03/26)
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- Optimization, Structure-Activity Relationship, and Mode of Action of Nortopsentin Analogues Containing Thiazole and Oxazole Moieties
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Plant diseases seriously endanger plant health, and it is very difficult to control them. A series of nortopsentin analogues were designed, synthesized, and evaluated for their antiviral activities and fungicidal activities. Most of these compounds displayed higher antiviral activities than ribavirin. Compounds 1d, 1e, and 12a, with excellent antiviral activities, emerged as novel antiviral lead compounds, among which 1e was selected for further antiviral mechanism research. The mechanism research results indicated that these compounds may play an antiviral role by aggregating viral particles to prevent their movement in plants. Further fungicidal activity tests revealed that nortopsentin analogues displayed broad-spectrum fungicidal activities. Compounds 2p and 2f displayed higher antifungal activities against Alternaria solani than the commercial fungicides carbendazim and chlorothalonil. Current research has laid a foundation for the application of nortopsentin analogues in plant protection.
- Guo, Jincheng,Hao, Yanan,Ji, Xiaofei,Wang, Ziwen,Liu, Yuxiu,Ma, Dejun,Li, Yongqiang,Pang, Huailin,Ni, Jueping,Wang, Qingmin
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p. 10018 - 10031
(2019/10/05)
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- Iridium(I)-Catalyzed C?H Borylation in Air by Using Mechanochemistry
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Mechanochemistry has been applied for the first time to an iridium(I)-catalyzed C?H borylation reaction. By using either none or just a catalytic amount of a liquid, the mechanochemical C?H borylation of a series of heteroaromatic compounds proceeded in air to afford the corresponding arylboronates in good-to-excellent yields. A one-pot mechanochemical C?H borylation/Suzuki–Miyaura cross-coupling sequence for the direct synthesis of 2-aryl indole derivatives is also described. The present study constitutes an important milestone towards the development of industrially attractive solvent-free C?H bond functionalization processes in air.
- Pang, Yadong,Ishiyama, Tatsuo,Kubota, Koji,Ito, Hajime
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supporting information
p. 4654 - 4659
(2019/03/17)
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- Dearomatization of 3-Nitroindoles with Highly γ-Functionalized Allenoates in Formal (3+2) Cycloadditions
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3-Nitroindoles are easily reacted with highly substituted γ-allenoates in the presence of a commercially available phosphine catalyst. For instance, allenoates derived from biomolecules such as amino and deoxycholic acids are combined for the first time w
- Birbaum, Léo,Gillard, Laurent,Gérard, Hélène,Oulyadi, Hassan,Vincent, Guillaume,Moreau, Xavier,De Paolis, Michael,Chataigner, Isabelle
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supporting information
p. 13688 - 13693
(2019/11/03)
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- Modular Synthesis of Di- A nd Trisubstituted Imidazoles from Ketones and Aldehydes: A Route to Kinase Inhibitors
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A one-pot and modular approach to the synthesis of 2,4(5)-disubstituted imidazoles was developed based on ketone oxidation, employing catalytic HBr and DMSO, followed by imidazole condensation with aldehydes. This methodology afforded twenty-nine disubstituted NH-imidazoles (23%-85% yield). A three-step synthesis of 20 kinase inhibitors was achieved by employing this oxidation-condensation protocol, followed by bromination and Suzuki coupling in the imidazole ring to yield trisubstituted NH-imidazoles (23%-69%, three steps). This approach was also employed in the synthesis of known inhibitor GSK3037619A.
- De Toledo, Ian,Grigolo, Thiago A.,Bennett, James M.,Elkins, Jonathan M.,Pilli, Ronaldo A.
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supporting information
p. 14187 - 14201
(2019/10/16)
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- Synthesis, antimicrobial and cytotoxic activities, and molecular docking studies of N-arylsulfonylindoles containing an aminoguanidine, a semicarbazide, and a thiosemicarbazide moiety
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Thirty-six N-arylsulfonyl-3-substituted indoles were designed and synthesized by combining the N-arylsulfonylindoles with aminoguanidine, semicarbazide, and thiosemicarbazide, respectively. Their antibacterial activities were screened, and cytotoxic activities were evaluated. The results showed that aminoguanidines (6) exhibited much better antibacterial activity than semicarbazides (7) and thiosemicarbazides (8). Most compounds in series 6 showed potent inhibitory activity against the tested bacterial strains, including multidrug-resistant strains, with MIC values in the range of 1.08–23.46 μM. The cytotoxic activity of the compounds 6c, 6d, 6h, 6j, 6k and 6l was assessed in two human cancer cell lines A590 and SGC7901, and one human normal cell line HEK 293T. The results indicated that compounds selected exhibited excellent activity against the tested cancer cells with IC50 values in the range of 1.51–15.12 μM suggesting the potential of them as new antibacterial and anticancer agents. What's more, the results of resistance study revealed that resistance of the tested bacteria toward 6d is not easily developed. Molecular docking studies revealed that the aminoguanidine and arylsulfonylindole moieties played a significant role in binding the target site of E. coli FabH-CoA receptor.
- Song, Mingxia,Wang, Shiben,Wang, Zengtao,Fu, Zhiyang,Zhou, Shengchao,Cheng, Huabin,Liang, Zhuo,Deng, Xianqing
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p. 108 - 118
(2019/01/28)
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- Insecticidal activity of indole derivatives against Plutella xylostella and selectivity to four non-target organisms
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The diamondback moth Plutella xylostella (Linnaeus, 1758) (Lepidoptera: Plutellidae) is a destructive pest of brassica crops of economic importance that have resistance to a range of insecticides. Indole derivates can exert diverse biological activities, and different effects may be obtained from small differences in their molecular structures. Indole is the parent substance of a large number of synthetic and natural compounds, such as plant and animal hormones. In the present study, we evaluate the insecticidal activity of 20 new synthesized indole derivatives against P. xylostella, and the selectivity of these derivatives against non-target hymenopteran beneficial arthropods: the pollinator Apis mellifera (Linnaeus, 1758) (Hymenoptera: Apidae), and the predators Polybia scutellaris (White, 1841), Polybia sericea (Olivier, 1791) and Polybia rejecta (Fabricius, 1798) (Hymenoptera: Vespidae). Bioassays were performed in the laboratory to determine the lethal and sublethal effects of the compounds on P. xylostella and to examine their selectivity to non-target organisms by topical application and foliar contact. The treatments consisted of two synthesized derivatives (most and least toxic), the positive control (deltamethrin) and the negative control (solvent). The synthesized compound 4e [1-(1H-indol-3-yl)hexan-1-one] showed high toxicity (via topical application and ingestion) and decreased the leaf consumption by P. xylostella, displaying a higher efficiency than the pyrethroid deltamethrin, widely used to control this pest. In addition, the synthesized indole derivatives were selective to the pollinator A. mellifera and the predators P. scutellaris, P. sericea and P. rejecta, none of which were affected by deltamethrin. Our results highlight the promising potential of the synthesized indole derivatives for the generation of new chemical compounds for P. xylostella management.
- Costa, ?ngela C. F.,Cavalcanti, Sócrates C. H.,Santana, Alisson S.,Lima, Ana P. S.,Brito, Thaysnara B.,Oliveira, Rafael R. B.,Macêdo, Nathália A.,Cristaldo, Paulo F.,Araújo, Ana Paula A.,Bacci, Leandro
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p. 973 - 982
(2019/08/26)
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- Optimizing ligand structure for low-loading and fast catalysis for alkynyl-alcohol and-amine cyclization
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A series of [Ru(Cp/Cp?)(PR2NR′2)(MeCN)]PF6 complexes were prepared, in which the steric and electronic properties of the primary coordination sphere were varied (R = Ph, t-Bu, Bn; and Cp vs. Cp?). These complexes were catalytically active in the cyclization of alkyne substrates with an intramolecular nucleophile (amine or alcohol) to produce 5-and 6-membered heterocycles. The effect of the 1° coordination sphere structure on catalyst performance was evaluated. Steric bulk around the metal centre was a key feature to achieve rapid catalysis at low temperatures. The catalyst [Ru(Cp)(Pt-Bu2NPh2)(MeCN)]PF6 gave a turnover number that was >1 order of magnitude more active than previous catalysts in the cyclization of the benchmark substrate 2-ethynylaniline. This catalyst is tolerant of a diversity of functional groups and is competent at the formation of various substituted indoles.
- Stubbs, James M.,Bridge, Benjamin J.,Blacquiere, Johanna M.
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p. 7928 - 7937
(2019/06/13)
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- Highly Robust but Surface-Active: An N-Heterocyclic Carbene-Stabilized Au25 Nanocluster
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Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active for liquid-phase catalysis without
- Shen, Hui,Deng, Guocheng,Kaappa, Sami,Tan, Tongde,Han, Ying-Zi,Malola, Sami,Lin, Shui-Chao,Teo, Boon K.,H?kkinen, Hannu,Zheng, Nanfeng
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p. 17731 - 17735
(2019/11/13)
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- MIL-101 supported highly active single-site metal catalysts for tricomponent coupling
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Metal-organic frameworks with regular pore structures provide powerful platforms for the design of single-site metal catalysts for chemical transformation. In this paper, we develop a facile, stable and recyclable MOF-supported Cu(II) catalyst, MIL-101-SO3Cu. It shows extremely high activity for the A3 coupling of alkynes, aldehydes and amines. The turnover frequency can reach 6.8 × 105 h?1 under neat conditions, which is the highest so far reported for the reaction. The high activity is because the specific structure of the MIL-101-SO3 support enables a single-site dispersion and an unhindered open environment for the metal ion. MIL-101-SO3Cu also exhibits high activity for the one-pot cascade reactions combining A3 coupling and 5-endo-dig cyclization.
- Sun, Weng-Jie,Gao, En-Qing
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p. 110 - 116
(2018/11/10)
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- Method for removing sulfinyl group in heteroaryl compound
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The invention discloses a method for removing a sulfinyl group in a heteroaryl compound. The method is characterized in that a heteroaryl cyclic sulfoxide compound represented by formula (Ia) or formula (Ib) and trimethylsilylphenyl trifluoromethanesulfonate represented by formula (II) used a substrate are reacted in the presence of cesium fluoride to obtain a sulfinyl group-removed heteroaryl compound represented by formula (IIIa) or (IIIb). The method can rapidly remove the sulfinyl group in the heteroaryl cyclic sulfoxide compound, does not need a metal catalyst with poor safety or highly toxic organic reagents, and is safe. The method has the advantages of mild conditions, strong compatibility with some sensitive benzenesulfonyl groups and Boc groups, simplicity in post-treatment, andsuitableness for industrial production.
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Paragraph 0025-0028; 0033-0036
(2019/10/01)
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- Desulfurization of Diaryl(heteroaryl) Sulfoxides with Benzyne
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Two benzyne-enabled desulfurization reactions have been demonstrated which convert diaryl sulfoxides and heteroaryl sulfoxides to biaryls and desulfurized heteroarenes, respectively. The reaction accessing biaryls tolerates a variety of functional groups, such as halides, pseudohalides, and carbonyls. Mechanistic studies reveal that both reactions proceed via a common assembly process but divergent disassemblies of the generated tetraaryl(heteroaryl) sulfuranes.
- Chen, De-Li,Sun, Yan,Chen, Mengyuan,Li, Xiaojin,Zhang, Lei,Huang, Xin,Bai, Yihui,Luo, Fang,Peng, Bo
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supporting information
(2019/06/13)
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- Electrochemically Enabled C3-Formylation and -Acylation of Indoles with Aldehydes
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Reported herein is an effective strategy for oxidative cross-coupling of indoles with various aldehydes. The strategy is based on a two-step transformation via a well-known Mannich-type reaction and a C-N bond cleavage for carbonyl introduction. The key step - the C-N bond cleavage of the Mannich product - was enabled by electrochemistry. This strategy (with over 40 examples) ensures excellent functional-group tolerance as well as late-stage functionalization of pharmaceutical molecules.
- Yang, Liquan,Liu, Zhaoran,Li, Yujun,Lei, Ning,Shen, Yanling,Zheng, Ke
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supporting information
p. 7702 - 7707
(2019/10/19)
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- Pd-tBuONO Cocatalyzed Aerobic Indole Synthesis
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A Pd-tBuONO co-catalyzed scalable and practical synthesis of indoles with molecular oxygen as terminal oxidant is developed. Either terminal or internal 2-vinylanilines could be smoothly converted to desired indoles under one general condition. This method has been evaluated in the large scale synthesis of indomethacin and a potential anti-breast cancer drug candidate 1. (Figure presented.).
- Ning, Xiao-Shan,Liang, Xin,Hu, Kang-Fei,Yao, Chuan-Zhi,Qu, Jian-Ping,Kang, Yan-Biao
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supporting information
p. 1590 - 1594
(2018/04/30)
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- Marine-Natural-Product Development: First Discovery of Nortopsentin Alkaloids as Novel Antiviral, Anti-phytopathogenic-Fungus, and Insecticidal Agents
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Nortopsentin alkaloids were found to have potent antiviral, anti-phytopathogenic-fungus, and insecticidal activities for the first time. Antiviral-activity tests revealed that these compounds were very sensitive to substituents, so a series of nortopsentin derivatives were designed, synthesized, and systematically evaluated for their antiviral activities against TMV, their fungicidal activities, and their insecticidal activities on the basis of a structural-diversity-derivation strategy. Compounds 2e (in vivo inactivation-, curative-, and protective-activity inhibitory rates of 50, 59, and 56%, respectively, at 500 μg/mL) and 2k (in vivo inactivation-, curative-, and protective-activity inhibitory rates of 60, 58, and 52%, respectively, at 500 μg/mL), with excellent antiviral activities and good physicochemical properties, emerged as new lead compounds for novel-antiviral-agent development. Further fungicidal-activity tests revealed that these alkaloids displayed broad-spectrum fungicidal activities. Compounds 2f, 2h, and 2j emerged as new lead compounds for antifungal-activity research. Additionally, all the compounds displayed good insecticidal activities against five kinds of insects, including Mythimna separate, Helicoverpa armigera, Ostrinia nubilalis, Plutella xylostella, and Culex pipiens pallens.
- Ji, Xiaofei,Guo, Jincheng,Liu, Yuxiu,Lu, Aidang,Wang, Ziwen,Li, Yongqiang,Yang, Shaoxiang,Wang, Qingmin
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p. 4062 - 4072
(2018/05/03)
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- Practical and Scalable Synthesis of Borylated Heterocycles Using Bench-Stable Precursors of Metal-Free Lewis Pair Catalysts
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A practical and scalable metal-free catalytic method for the borylation and borylative dearomatization of heteroarenes has been developed. This synthetic method uses inexpensive and conveniently synthesizable bench-stable precatalysts of the form 1-NHR2-2-BF3-C6H4, commercially and synthetically accessible heteroarenes as substrates, and pinacolborane as the borylation reagent. The preparation of several borylated heterocycles on 2 and 50 g scales was achieved under solvent-free conditions without the use of Schlenk techniques or a glovebox. A kilogram-scale borylation of one of the heteroarene substrates was also achieved using this cost-effective green methodology to exemplify the fact that our methodology can be conveniently implemented in fine chemical industries.
- Jayaraman, Arumugam,Misal Castro, Luis C.,Fontaine, Frédéric-Georges
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supporting information
p. 1489 - 1499
(2018/10/26)
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- A indole compound and its preparation method and application (by machine translation)
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The invention discloses a indole compound and its preparation method and application. The indole compounds of the structural formula such as formula (I) is shown. The indoles, rice galenical demonstrate the excellent inhibitory activity, the effect of most of the compound is obviously better than the positive control drug validamycin; especially compound I - 43, I - 44, I - 54, I - 73, II - 7 and II - 17, its galenical very good living body protection and treating effect, effect is better than the positive control; more specifically, compound I - 43 of the rice sheath blight bacteriostatic activity than validamycin activity is improved by nearly 300 times. The indole compounds in the prevention and/or treatment of rice sheath blight has great application prospects. In addition the compound of the invention is simple in construction, the preparation method is simple, and is suitable for large-scale industrial production. (I). (by machine translation)
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Paragraph 0092; 0093
(2018/10/02)
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- N - substituted benzene sulfonyl -3 - propionyl indole derivatives, preparation method and application
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The invention discloses an N-substituted benzenesulfonyl-3-propionyl indole derivative, a preparation method and application and belongs to the technical field of organic synthesis. The structural formula of the N-substituted benzenesulfonyl-3-propionyl i
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Paragraph 0189-0193
(2018/07/30)
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- Ring-Opening of Indoles: An Unconventional Route for the Transformation of Indoles to 1 H-Pyrazoles Using Lewis Acid
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An unusual transformation of indoles to pyrazoles via an aromatic ring-opening strategy has been developed. The salient feature of this strategy involves the C2-N1 bond opening and concomitant cyclization reaction of the C2=C3 bond of the indole moiety with the tosylhydrazone, which proceeds under transition-metal and ligand free conditions. This ring-opening functionalization of indoles provides a wide scope of differently substituted pyrazoles.
- Panda, Subhankar,Pradhan, Nirmalya,Manna, Debasis
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supporting information
p. 573 - 578
(2018/09/25)
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- Mild alkaline hydrolysis of hindered esters in non-aqueous solution
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Sterically hindered esters of carboxylic acids, which are considered very resistant to saponification, were rapidly and efficiently saponified in a non-aqueous medium using NaOH in MeOH/CH2Cl2 (1:9) at room temperature. Furthermore, this reaction protocol was extended and successfully applied to the hydrolysis of tosylates and N-tosyl indoles.
- Theodorou, Vassiliki,Alagiannis, Michalis,Ntemou, Nikoleta,Brentas, Alexios,Voulgari, Pinelopi,Polychronidou, Vasiliki,Gogou, Marina,Giannelos, Marios,Skobridis, Konstantinos
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p. 308 - 319
(2018/11/26)
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- Trimethylphosphate as a Methylating Agent for Cross Coupling: A Slow-Release Mechanism for the Methylation of Arylboronic Esters
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A methyl group on an arene, despite its small size, can have a profound influence on biologically active molecules. Typical methods to form a methylarene involve strong nucleophiles or strong and often toxic electrophiles. We report a strategy for a new, highly efficient, copper and iodide co-catalyzed methylation of aryl- and heteroarylboronic esters with the mild, nontoxic reagent trimethylphosphate, which has not been used previously in coupling reactions. We show that it reacts in all cases tested in yields that are higher than those of analogous copper-catalyzed reactions of MeOTs or MeI. The combination of C-H borylation and this methylation with trimethylphosphate provides a new approach to the functionalization of inert C-H bonds and is illustrated by late-stage methylation of four medicinally active compounds. In addition, reaction on a 200 mmol scale demonstrates reliability of this method. Mechanistic studies show that the reaction occurs by a slow release of methyl iodide by reaction of PO(OMe)3 with iodide catalyst, rather than the typical direct oxidative addition to a metal center. The low concentration of the reactive electrophile enables selective reaction with an arylcopper intermediate, rather than nucleophilic groups on the arylboronate, and binding of tert-butoxide to the boronate inhibits reaction of the electrophile with the tert-butoxide activator to form methyl ether.
- He, Zhi-Tao,Li, Haoquan,Haydl, Alexander M.,Whiteker, Gregory T.,Hartwig, John F.
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supporting information
p. 17197 - 17202
(2018/12/14)
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- Metal-Free Oxidative Cross Coupling of Indoles with Electron-Rich (Hetero)arenes
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A new method for the synthesis of bi-heteroaryls is reported, based on the umpolung of indoles with benziodoxol(on)e hypervalent iodine reagents (IndoleBX). The oxidative coupling of IndoleBX with an equimolar amount of electron-rich benzenes, indoles, pyrroles, and thiophenes proceeded under mild transition-metal-free conditions. Functionalized non-symmetrical bi-indolyl heterocycles were accessed efficiently. Introduction of a new type of C2-substituted indole benziodoxole reagents further allowed extending the scope of the reaction to NH unprotected and C3-alkylated indoles. The obtained bi-heterocycles are important building blocks in synthetic and medicinal chemistry, and could be easily transformed into more complex heterocyclic systems.
- Caramenti, Paola,Nandi, Raj Kumar,Waser, Jerome
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supporting information
p. 10049 - 10053
(2018/07/29)
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- Directly Bridging Indoles to 3,3′-Bisindolylmethanes by Using Carboxylic Acids and Hydrosilanes under Mild Conditions
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A straightforward Lewis acid-promoted protocol for 3,3′-bisindolylmethanes (BIMs) synthesis by reductive alkylation of indoles at the C3 position with carboxylic acids in the presence of hydrosilane was developed for the first time. Instead of aldehydes, more readily available, stable, and easy-to-handle carboxylic acids have been employed as alternative alkylating agents. As an efficient organocatalyst, B(C6F5)3 enables the reductive alkylation of various substituted indole derivatives with carboxylic acids with up to 98 % yield at room temperature and under neat conditions. This metal-free strategy offers an alternative approach for the direct functionalization of indoles to BIMs with carboxylic acids and such protocol allows selective reduction of carboxylic acid to aldehyde in combination with C?C bond formation.
- Qiao, Chang,Liu, Xiao-Fang,Fu, Hong-Chen,Yang, Hao-Peng,Zhang, Zhi-Bo,He, Liang-Nian
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p. 2664 - 2670
(2018/09/14)
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- CuCl2/[hmim]Br: A new recyclable catalytic system for aromatization of cyclic dienes
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The combination of copper(II) chloride and 1-hexyl-3-methylimidazolium bromide ([hmim]Br) as a new recyclable catalytic system in the presence of TBHP for aromatization of cyclic dienes is disclosed. The system could furnish the corresponding aromatics in moderate to excellent yield. The competition between aromatization and oxidation of benzylic substrates were also studied. This developed catalytic system could be reused and recycled at least nine times without significant loss of the producitivity.
- Taboonpong, Piyada,Chavasiri, Warinthorn
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- Method for cyclization reaction to synthesize indole through co-catalysis of palladium-organic nitrite
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The invention discloses a method for cyclization reaction to synthesize indole through co-catalysis of palladium-organic nitrite. The method is characterized by comprising the steps of mixing at the molar ratio of a palladium compound to a 2-vinyl aniline
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Paragraph 0019-0021
(2017/09/18)
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- Facile synthesis of indoles by K2CO3catalyzed cyclization reaction of 2-ethynylanilines in water
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The cyclization reaction of 2-ethynyl-N-sulfonylanilides proceeded efficiently in water with the presence of a catalytic amount of K2CO3under transition metal-free condition to give indoles in high yields. The recovery and reusabilit
- Chen, Zhi,Shi, Xiao-Xiao,Ge, Dong-Qin,Jiang, Zhen-Zhen,Jin, Qi-Qi,Jiang, Hua-Jiang,Wu, Jia-Shou
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supporting information
p. 231 - 234
(2017/01/28)
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- A concise approach to indoles via oxidative C-H amination of 2-alkenylanilines using dioxygen as the sole oxidant
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A novel synthetic method to prepare indole derivatives from N-Ts-2-alkenylanilines has been achieved. This reaction is through an oxidative intramolecular C-H amination by using molecular oxygen as the sole oxidant. This protocol is operationally simple a
- Ma, Ai-Lun,Li, Yin-Long,Li, Jian,Deng, Jun
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p. 35764 - 35770
(2016/05/19)
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- Catalytic, Interrupted Formal Homo-Nazarov Cyclization with (Hetero)arenes: Access to α-(Hetero)aryl Cyclohexanones
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The first examples of a Lewis-acid catalyzed (hetero)arene interrupted, formal homo-Nazarov cyclization have been disclosed. Using SnCl4 as the catalyst, alkenyl cyclopropyl ketones undergo ring-opening cyclization to form six-membered cyclic oxyallyl cations. Subsequent intermolecular Friedel-Crafts-type arylation with various electron-rich arenes and heteroarenes provides functionalized α-(hetero)arylated cyclohexanones, a scaffold present in many natural products and bioactive compounds, in yields up to 88% and diastereomeric ratios up to 12:1. Regiospecific arylation occurs at the α-carbon of the oxyallyl cation due to polarization caused by the ester group.
- Williams, Corey W.,Shenje, Raynold,France, Stefan
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p. 8253 - 8267
(2016/09/28)
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- Pushing the Limits of Neutral Organic Electron Donors: A Tetra(iminophosphorano)-Substituted Bispyridinylidene
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A new ground-state organic electron donor has been prepared that features four strongly π-donating iminophosphorano substituents on a bispyridinylidene skeleton. Cyclic voltammetry reveals a record redox potential of ?1.70 V vs. saturated calomel electrode (SCE) for the couple involving the neutral organic donor and its dication. This highly reducing organic compound can be isolated (44 %) or more conveniently generated in situ by a deprotonation reaction involving its readily prepared pyridinium ion precursor. This donor is able to reduce a variety of aryl halides, and, owing to its redox potential, was found to be the first organic donor to be effective in the thermally induced reductive S N bond cleavage of N,N-dialkylsulfonamides, and reductive hydrodecyanation of malonitriles.
- Hanson, Samuel S.,Doni, Eswararao,Traboulsee, Kyle T.,Coulthard, Graeme,Murphy, John A.,Dyker, C. Adam
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p. 11236 - 11239
(2016/07/06)
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- Catalytic C-2 Allylation of Indoles by Electronic Modulation of the Indole Ring and its Application to the Synthesis of Functionalized Carbazoles
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We report a palladium-catalyzed C-2 allylation of indoles and subsequent cyclization of the allylated indoles. The electronic effects of chloro and ester groups that can be readily installed at the C-3 position of indoles facilitated a highly efficient C–H allylation at the C-2 position. The resulting 2-allyl-3-chloroindoles were found to be suitable substrates for benzannulation reactions with alkynes and norbornadiene as an acetylene synthon. This approach, utilizing readily available indoles, allyl acetates, and norbornadiene, allows a rapid access to complex carbazoles. (Figure presented.).
- Lee, Ju Young,Ha, Hyeri,Bae, Seri,Han, Inhyuk,Joo, Jung Min
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p. 3458 - 3470
(2016/11/13)
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- CONDENSED BICYCLIC HETEROCYCLIC DERIVATIVE
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PROBLEM TO BE SOLVED: To provide a compound having excellent retinoic acid receptor related orphan receptor γt inhibition effect and useful as a therapeutic agent for psoriasis or the like. SOLUTION: There is provided a compound represented by the general
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Paragraph 0493; 0495
(2018/09/12)
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- Silver(I)-mediated C-H amination of 2-alkenylanilines: Unique solvent-dependent migratory aptitude
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A highly effective silver(I)-mediated C-H amination of 2-alkenylanilines has been developed to afford a diverse range of substituted indoles. High functional group tolerance, broad substrate scope, simple/fast/high-yielding reaction, and recovery/reuse of the inexpensive silver oxidant are noteworthy. Furthermore, an uncommon migratory process of β-monosubstituted 2-alkenylanilines with solvent-dependence was demonstrated.
- Youn, So Won,Ko, Tae Yun,Jang, Min Jung,Jang, Su San
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supporting information
p. 227 - 234
(2015/01/30)
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- Stereoselective synthesis of cis-2,6-disubstituted morpholines and 1,4-oxathianes by intramolecular reductive etherification of 1,5-diketones
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A simple and efficient, Lewis acid catalysed reductive etherification strategy for the stereoselective synthesis of cis-2,6- disubstituted morpholines and 1,4-oxathianes starting from readily available 1,5-diketones has been developed. The strategy is used in the total synthesis of morpholine-based natural products (±)-chelonin A and formal total synthesis of (±)-chelonin C.
- Gharpure, Santosh J.,Anuradha, Dandela,Prasad, Jonnalagadda V. K.,Rao, Pidugu Srinivasa
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supporting information
p. 86 - 90
(2015/01/16)
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- TFA-promoted direct C-H sulfenylation at the C2 position of non-protected indoles
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A simple, efficient and practical metal-free C-H sulfenylation process at the C2 position of non-protected indoles has been developed. 2-Thioindoles were obtained in moderate to high yields using stable and readily available N-(thio)succinimides at room temperature in the presence of TFA.
- Hostier, Thomas,Ferey, Vincent,Ricci, Gino,Pardo, Domingo Gomez,Cossy, Janine
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supporting information
p. 13898 - 13901
(2015/09/07)
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