- Application of SBA-Pr-NH2 as a nanoporous base silica catalyst in the development of 2,2-Bis(1H-indol-3-yl)acenaphthen-1(2H)-ones syntheses
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One-pot reaction for the synthesis of symmetrical 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one is reported by condensing acenaphthenequinone and indoles in the presence of catalytic amount of amino-functionalized silica (SBA-Pr-NH2) under solvent-free conditions at 100°C. (Chemical Equation Presented).
- Mohammadi Ziarani,Hajiabbasi,Badiei
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- Structure and Reactivity of Indolylmethylium Ions: Scope and Limitations in Synthetic Applications
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Eight substituted aryl(indol-3-yl)methylium tetrafluoroborates 3(a-h)-BF4 and three bis(indol-3-yl)methylium tetrafluoroborates 3(i-k)-BF4 have been synthesized and characterized by NMR spectroscopy and X-ray crystallography. Their reactions with π-nucleophiles 8(a-j) (silylated enol ethers and ketene acetals) were studied kinetically using photometric monitoring at 20 °C. The resulting second-order rate constants were found to follow the correlation log k(20 °C) = sN(N + E), in which nucleophiles are characterized by the two solvent-dependent parameters N and sN, and electrophiles are characterized by one parameter, E. From the previously reported N and sN parameters of the employed nucleophiles and the measured rate constants, the electrophilicities of the indol-3-ylmethylium ions 3(a-k) were derived and used to predict potential nucleophilic reaction partners. A discrepancy between published rate constants for the reactions of morpholine and piperidine with the (2-methylindol-3-yl)phenylmethylium ion 3h and those calculated from E, N, and sN was analyzed and demonstrated to be due to a mistake of the value reported in the literature.
- Follet, Elsa,Berionni, Guillaume,Mayer, Peter,Mayr, Herbert
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- Regioselective Fischer indole synthesis mediated by organoaluminum amides
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Amphiphilic reagents such as organoaluminum amides are found to be highly effective for the Fischer indole synthesis. In particular, diethylaluminum 2,2,6,6-tetramethylpiperidide (DATMP) is the reagent of choice for regioselective Fischer indole synthesis. For example, treatment of the (E)- N-methyl-N-phenylhydrazone of 5-methyl-3-heptanone with DATMP affords 3-sec- butyl-2-ethyl-1-methylindole as the sole isolable product; its Z-isomer affords 1,3-dimethyl-2-(2-methylbutyl)indole with high regioselectivity under similar reaction conditions.
- Maruoka,Oishi,Yamamoto
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- Potassium tert-Butoxide-Catalyzed Dehydrogenative C-H Silylation of Heteroaromatics: A Combined Experimental and Computational Mechanistic Study
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We recently reported a new method for the direct dehydrogenative C-H silylation of heteroaromatics utilizing Earth-abundant potassium tert-butoxide. Herein we report a systematic experimental and computational mechanistic investigation of this transformation. Our experimental results are consistent with a radical chain mechanism. A trialkylsilyl radical may be initially generated by homolytic cleavage of a weakened Si-H bond of a hypercoordinated silicon species as detected by IR, or by traces of oxygen which can generate a reactive peroxide by reaction with [KOt-Bu]4 as indicated by density functional theory (DFT) calculations. Radical clock and kinetic isotope experiments support a mechanism in which the C-Si bond is formed through silyl radical addition to the heterocycle followed by subsequent β-hydrogen scission. DFT calculations reveal a reasonable energy profile for a radical mechanism and support the experimentally observed regioselectivity. The silylation reaction is shown to be reversible, with an equilibrium favoring products due to the generation of H2 gas. In situ NMR experiments with deuterated substrates show that H2 is formed by a cross-dehydrogenative mechanism. The stereochemical course at the silicon center was investigated utilizing a 2H-labeled silolane probe; complete scrambling at the silicon center was observed, consistent with a number of possible radical intermediates or hypercoordinate silicates.
- Liu, Wen-Bo,Schuman, David P.,Yang, Yun-Fang,Toutov, Anton A.,Liang, Yong,Klare, Hendrik F. T.,Nesnas, Nasri,Oestreich, Martin,Blackmond, Donna G.,Virgil, Scott C.,Banerjee, Shibdas,Zare, Richard N.,Grubbs, Robert H.,Houk,Stoltz, Brian M.
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- Potassium carbonate as a base for the N-alkylation of indole and pyrrole in ionic liquids
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The methodology for the N-alkylation of indole and pyrrole using potassium carbonate in 1-n-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF4] as the sustainable reaction media with acetonitrile as the cosolvent is described herein. Our approach provides good yields with alkyl halides as well as sulfonates as the electrophiles. Cesium carbonate was also found to be a consistent base in the N-alkylation. The proposed methodology is simple and mild with easy workup.
- Jorapur, Yogesh R.,Jeong, Jae Min,Chi, Dae Yoon
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- Oxidation of Tryptophan and N-Methylindole by N3*, Br2*-, and (SCN)2*- Radicals in Light- and Heavy-Water Solutions: A Pulse Radiolysis Study
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Reactions of N3*, Br2*-, and (SCN)2*- with tryptophan (TRPH) and N-methylindole (NMI) have been investigated in H2O and D2O solutions.The main transients produced were the TRP* radical and the TRPH*+ radical cation from TRPH and the NMI*+ radical cation from NMI.Their extinction coefficients (ε) as well as the rate constants for their formation and decay were determined in the pH range 3-10.The pK of the TRPH*+ radical cation was confirmed to be 4.2 +/- 0.1.These rate constants were within experimental error, independent of pH, and the differences between the rate constants in H2O and D2O were small.On the basis of the results, it was concluded that of the two possible reactions - electron or hydrogen atom transfer - the data are more consistent with electron transfer in all cases.However, secondary acid-base reactions have an important effect on the overall redox equilibria, especially with N3*.Experimental data on these effects have also been obtained.
- Solar, Sonja,Getoff, Nikola,Surdhar, Parminder S.,Armstrong, David A.,Singh, Ajit
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- Rhodium(III)-Catalyzed Regioselective C?H Allylation and Prenylation of Indoles at C4-Position
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Herein, Rh(III)-catalyzed C4-selective C?H allylation and prenylation of indoles by using a weak carbonyl coordination directing group have been reported. By employing 5-methylene-1,3-dioxan-2-ones, 4-vinyl-1,3-dioxolan-2-ones and 2-methyl-2,3-butadiene as scalable cross-coupling partners, these divergent synthesis protocols proceed smoothly under redox-neutral reaction conditions, delivering various allylated and prenylated indoles in moderate to satisfied yields. This transformation exhibits high functional-groups compatibility and broad substrate scope. Scale-up experiment and mechanistic studies were also accomplished. (Figure presented.).
- Zhang, Shang-Shi,Liu, Yan-Zhi,Zheng, Yi-Chuan,Xie, Hui,Chen, Shao-Yong,Song, Jia-Lin,Shu, Bing
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supporting information
p. 64 - 70
(2021/11/03)
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- Synthesis of Non-Terminal Alkenyl Ethers, Alkenyl Sulfides, and N-Vinylazoles from Arylaldehydes or Diarylketones, DMSO and O, S, N-Nucleophiles
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A transition-metal-free protocol for the synthesis of non-terminal alkenyl ethers, alkenyl sulfides, and N-vinylazoles from arylaldehydes or diarylketones, DMSO and O, S, N-nucleophiles has been reported. In this protocol, 24 examples of non-terminal alkenyl ethers and 28 examples of non-terminal alkenyl sulfides in 72–95% yields have been synthesized within 5 min. Moreover, 27 examples of non-terminal N-vinylazoles with 57–88% yields have also been synthesized within 2 hours. The preliminary mechanism investigations revealed that arylaldehydes or diarylketones offered a carbon atom, DMSO provided a methine and O, S, N-nucleophiles contributed one X atom for constructing C=C?X structure. (Figure presented.).
- Nie, Zhiwen,Lv, Huifang,Yang, Tonglin,Su, Miaodong,Luo, Weiping,Liu, Qiang,Guo, Cancheng
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supporting information
p. 1473 - 1480
(2022/04/03)
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- Preparation method of nitrogen-alkyl (deuterated alkyl) aromatic heterocycle and alkyl (deuterated alkyl) aryl ether compound
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The invention provides a method for preparing nitrogen-alkyl(deuterated alkyl)aromatic heterocycle and alkyl(deuterated alkyl)aryl ether compounds. The method adopted in the invention specifically comprises the following steps: firstly, adding an alkoxy base (MOR') or a combination reagent Q (comprising a base M'X, an alcohol C and a molecular sieve E) into a solvent B to be stirred; then, addingan aromatic compound D of nitrogen sulfonyl or oxygen sulfonyl into a mixture; separating and purifying after reaction to obtain nitrogen-alkyl(deuterated alkyl)aromatic heterocycle or alkyl(deuterated alkyl)aryl ether. The method can realize one-step conversion from an electron withdrawing benzenesulfonyl protecting group on a nitrogen or oxygen atom to an electron donating alkyl protecting group, avoids using highly toxic alkyl halide, and has advantages of being efficient, economical, environmentally friendly, mild in condition, good in substrate universality and high in yield; the prepareddeuterated compounds can be widely applied to the fields of pharmaceutical chemistry and organic chemistry synthesis.
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Paragraph 0026-0029
(2021/04/03)
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- A Bottleable Imidazole-Based Radical as a Single Electron Transfer Reagent
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Reduction of 1,3-bis(2,6-diisopropylphenyl)-2,4-diphenyl-1H-imidazol-3-ium chloride (1) resulted in the formation of the first structurally characterized imidazole-based radical 2. 2 was established as a single electron transfer reagent by treating it with an acceptor molecule tetracyanoethylene. Moreover, radical 2 was utilized as an organic electron donor in a number of organic transformations such as in activation of an aryl-halide bond, alkene hydrosilylation, and in catalytic reduction of CO2 to methoxyborane, all under ambient temperature and pressure.
- Das, Arpan,Ahmed, Jasimuddin,Rajendran,Adhikari, Debashis,Mandal, Swadhin K.
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p. 1246 - 1252
(2020/12/21)
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- Synthesis of 1-indolyl-3,5,8-substituted γ-carbolines: one-pot solvent-free protocol and biological evaluation
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1,5-Disubstituted indole-2-carboxaldehyde derivatives 1a–h and glycine alkyl esters 2a–c are shown to undergo a novel cascade imination-heterocylization in the presence of the organic base DIPEA to provide 1-indolyl-3,5,8-substituted γ-carbolines 3aa–ea in good yields. The γ-carbolines are fluorescent and exhibit anticancer activities against cervical, lung, breast, skin, and kidney cancer cells.
- Chelvam, Venkatesh,Dudhe, Premansh,Krishnan, Mena Asha,Pathak, Biswarup,Roy, Diptendu,Venkatasubbaiah, Krishnan,Yadav, Kratika
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supporting information
p. 1453 - 1463
(2021/07/02)
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- Three-component reactions of 3-arylidene-3h-indolium salts, isocyanides and amines
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A multicomponent reaction of isocyanides with aryl(indol-3-yl)methylium salts and amines has been found. A series of aryl(indol-3-yl)acetimidamides was obtained in up to 96% yields. In the case of ethyl isocyanoacetate, the reaction is followed by cyclization to form 3,5-dihydro-4H-imidazol-4-one derivatives.
- Nguyen, Hung M.,Golantsov, Nikita E.,Golubenkova, Alexandra S.,Rybakov, Victor B.,Voskressensky, Leonid G.
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- 1,2,4-Oxadiazole Topsentin Analogs with Antiproliferative Activity against Pancreatic Cancer Cells, Targeting GSK3β Kinase
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A new series of topsentin analogs, in which the central imidazole ring of the natural lead was replaced by a 1,2,4-oxadiazole moiety, was efficiently synthesized. All derivatives were pre-screened for antiproliferative activity against the National Cancer Institute (NCI-60) cell lines panel. The five most potent compounds were further investigated in various pancreatic ductal adenocarcinoma (PDAC) cell lines, including SUIT-2, Capan-1, and Panc-1 cells, eliciting EC50 values in the micromolar and sub-micromolar range, associated with significant reduction of cell migration. These remarkable results might be explained by the effects of these new topsentin analogues on epithelial-to-mesenchymal transition markers, including SNAIL-1/2 and metalloproteinase-9. Moreover, flow cytometric analysis after Annexin V-FITC and propidium iodide staining demonstrated that these derivatives enhanced apoptosis of PDAC cells. Keeping with these data, the PathScan intracellular signaling and ELISA array revealed cleavage of caspase-3 and PARP and a significant inhibition of GSK3β phosphorylation, suggesting this kinase as a potential downstream target of our novel compounds. This was further supported by a specific assay for the evaluation of GSK3β activity, showing IC50 values for the most active compounds against this enzyme in the micromolar range.
- Carbone, Daniela,Parrino, Barbara,Cascioferro, Stella,Pecoraro, Camilla,Giovannetti, Elisa,Di Sarno, Veronica,Musella, Simona,Auriemma, Giulia,Cirrincione, Girolamo,Diana, Patrizia
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p. 537 - 554
(2020/12/01)
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- Tandem iridium-catalyzed decarbonylative c-h activation of indole: Sacrificial electron-rich ketone-assisted bis-arylsulfenylation
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Described herein is a decarbonylative tandem C-H bis-arylsulfenylation of indole at the C2 and C4 C-H bonds through the use of pentamethylcyclopentadienyl iridium dichloride dimer ([Cp?IrCl2]2) catalyst and disulfides. A new sacrificial electron-rich adamantoyl-directing group facilitates indole C-H bis-functionalization with a traceless in situ removal. Various differently substituted disulfides can be easily accommodated in this reaction by a coordination to Ir(III) through the formation of six- and five-membered iridacycles at the C2 and C4 positions, respectively. Mechanistic studies show that a C-H activation-induced C-C activation is involved in the catalytic cycle.
- Kathiravan, Subban,Anaspure, Prasad,Zhang, Tianshu,Nicholls, Ian A.
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supporting information
p. 3331 - 3336
(2021/05/29)
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- Assembly of polycyclic N-heterocycles: Via copper-catalyzed cycloamination of indolylquinones and aromatic amines
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The copper-catalyzed cycloamination of indolylquinones and various (hetero)aromatic amines under ligand-free conditions for the synthesis of polycyclic N-heterocycles has been developed. This method allows facile access to polycyclic N-heterocycles with the tolerance of chloride, bromide, amino, thio, etc. groups in moderate to high yields (60-89%).
- Dong, Yu,Mei, Ting,Ye, Ji-Xian,Chen, Xiang-Long,Jiang, Hui,Chang, Bo,Wang, Zhi-Fan,Shi, Zhi-Chuan,Li, Zhong-Hui,He, Bing
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supporting information
p. 4593 - 4598
(2021/05/31)
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- Visible-Light-Induced Carbonylation of Indoles with Phenols under Metal-Free Conditions: Synthesis of Indole-3-carboxylates
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A visible-light-induced carbonylation of indoles with phenols for the synthesis of indole-3-carboxylates has been developed. The reaction proceeded via a radical carbonylation process in which elementary I2 was used as an effective photosensitive initiator and, thus, avoided the use of transition metal catalysts. A series of different aryl indole-3-carboxylates were prepared in moderate to good yields. The broad applicability of this methodology was further highlighted by the late-stage functionalization of several phenol-containing natural products and pharmaceuticals.
- Qi, Zhuang,Li, Lin,Liang, Ying-Kang,Ma, Ai-Jun,Zhang, Xiang-Zhi,Peng, Jin-Bao
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supporting information
p. 4769 - 4773
(2021/06/28)
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- Copper-Catalyzed Synthesis of Indolyl Benzo[b]carbazoles and Their Photoluminescence Property
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A copper-catalyzed cascade cyclization of dihydroisobenzofurans with indoles for the rapid construction of indoly benzo[b]carbazoles has been reported, providing the desired products in moderate to good yields under mild conditions along with a broad substrate scope and good functional group tolerance. The photoluminescence property of these indoly benzo[b]carbazoles has also been investigated.
- Hao, Tonggang,Huang, Long,Wei, Yin,Shi, Min
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supporting information
p. 5133 - 5137
(2021/07/19)
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- Salicylaldehyde-Promoted Cobalt-Catalyzed C-H/N-H Annulation of Indolyl Amides with Alkynes: Direct Synthesis of a 5-HT3 Receptor Antagonist Analogue
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A cobalt-catalyzed annulation of the C(sp2)-H/N-H bond of indoloamides with alkynes assisted by 8-aminoquinoline is reported for the synthesis of six-membered indololactams. The use of salicylaldehyde as the ligand is crucial for this transformation. The protocol has a broad scope for both alkynes and indoles. Preparing an active Co complex illustrates that salicylaldehyde plays a key role in the C-H activation step. The synthetic applications are proven by the gram-scale reaction and one-step construction of the multicyclic 5-HT3 receptor antagonist.
- Huang, Mao-Gui,Shi, Shuai,Li, Ming,Liu, Yue-Jin,Liu, Yue-Jin
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supporting information
p. 7094 - 7099
(2021/09/14)
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- Application of biomass-supported copper-catalyzed three-component reaction in preparation of fluorine-containing drugs
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The invention relates to an application of a biomass-supported copper-catalyzed three-component reaction in preparation of a fluorine-containing drug. The indole and its derivatives and are synthesized 3 - (2 - (trifluoromethyl) - indo -3 -yl) quinoxaline -2 - ketone derivatives by one-pot synthesis by three-component one-pot method. To the invention, the heterogeneous biological substance carried copper catalyst is adopted to catalyze the reaction, and the problems that a traditional homogeneous catalyst cannot be recovered, metal residues are left and the like are solved. 3 - (2 - (Trifluoromethyl) - indo -3 -yl) quinoxaline -2 - ketone compounds with different substituents are expanded, and the biomass supported copper catalyst can be cyclically and catalytically reacted.
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Paragraph 0047; 0050; 0051
(2021/09/29)
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- Synthesis of 3-halogenated 2,3′-biindoles by a copper-mediated 2,3-difunctionalization of indoles
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A copper-mediated 2,3-difunctionalization of indoles to afford 3-halogenated 2,3′-biindoles is described herein. The protocol uses readily available feedstocks and a naturally abundant copper catalyst system, which allows the regioselective formation of C-C and C-X (X = Cl & Br) bonds in one single operation. Here the copper metal salt serves not only as a catalyst but also as a reactant to provide the source of halogen. This operationally simple procedure avoids the utilization of environmentally unfriendly reagents and displays good functional group compatibility. Noteworthily, the introduction of halogen into molecules would offer great potential for further chemical transformations. This journal is
- Gu, Xiaoting,Liang, Taoyuan,Wei, Wanxing,Zhang, Xiaoxiang,Zhang, Yingying,Zhang, Zhuan
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supporting information
p. 10403 - 10407
(2021/12/17)
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- Enantioconvergent Arylation of Racemic Secondary Alcohols to Chiral Tertiary Alcohols Enabled by Nickel/N-Heterocyclic Carbene Catalysis
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The direct upgrading reaction of simple and readily available achiral alcohols via C-H functionalization is an ideal strategy to prepare value-added chiral higher alcohols. Herein, we disclose the first enantioconvergent upgrading reaction of simple racemic secondary alcohols to enantioenriched tertiary alcohols. An N-heterocyclic carbene (NHC)-nickel catalyst was leveraged to enable this highly efficient formal asymmetric alcohol α-C-H arylation via a dehydrogenation using phenyl triflate as a mild oxidant followed by asymmetric addition of arylboronic esters to the transient ketones. Mechanistic studies and control experiments were conducted to reveal the possible reasons for the exceptional control over chemo- and enantioselectivity.
- Cai, Yuan,Shi, Shi-Liang
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supporting information
p. 11963 - 11968
(2021/08/20)
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- Origin of Stability and Inhibition of Cooperative Alkyne Hydrofunctionalization Catalysts
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New entries to the [Ru(Cp/Cp*)(PR2NR′2)(MeCN)]PF6 catalyst family were synthesized, including a Cp complex (R = Cy; R′ = Ph) and two Cp* complexes (R = Cy, Ph; R′ = Ph). These and other derivatives were used for the intramolecular hydroamination of 2-ethynylaniline to elucidate trends in catalytic lifetime and rate. The readily accessible [Ru(Cp)(PCy2NPh2)(MeCN)]PF6 derivative showed comparable lifetime to [Ru(Cp)(Pt?Bu2NPh2)(MeCN)]PF6, the previous optimal catalyst. Donor-free ‘active’ catalysts, [Ru(Cp/Cp*)(PCy2NPh2)]PF6, were prepared and their thermal stability was assessed. The relatively high stability of the Cp derivative was explained by the capacity of the PCy2NPh2 ligand to coordinate in a κ3-(P,P,Ar) mode, which protects the low-coordinate species. This coordination mode is inaccessible with the Cp* derivative. Additionally, [Ru(Cp*)(PCy2NPh2)]PF6 readily activated the C?Cl bond of the solvent dichloromethane. Variable time normalization analysis (VTNA) revealed that the indole product inhibited the catalyst [Ru(Cp)(PCy2NPh2)(MeCN)]PF6, which slowed catalytic rates.
- Chapple, Devon E.,Boyle, Paul D.,Blacquiere, Johanna M.
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p. 3789 - 3800
(2021/07/20)
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- Methylation synthesis method of N-heterocyclic compound
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The invention relates to a methylation synthesis method of an N-heterocyclic compound, which is characterized by comprising the following steps of a, methylation reaction: sequentially adding an N-heterocyclic compound and dimethyl carbonate into a reaction kettle, carrying out gas replacement, heating, keeping the temperature and pressure, and reacting, wherein the reaction temperature is 80-250DEG C, and the pressure is 0.3-8.0 MPa, and b, rectification: after the reaction is completed, reducing the pressure, carrying out reduced pressure rectification on the reaction mother liquor to obtain a methylation product, and recovering dimethyl carbonate and byproduct methanol. The dimethyl carbonate reagent is used for synthesizing the N-methylation product under the pressurization condition,and compared with methyl iodide and dimethyl sulfate, dimethyl carbonate is low in toxicity and more environmentally friendly; the reaction conversion rate is high, the operation is simple, and the reaction cost is low. Meanwhile, the methylation reaction selectivity is extremely good, and the method is suitable for high-selectivity synthesis of series products such as 1-methyl-1H-indole, 1, 3, 3-trimethyl-2-methylene indoline and the like.
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Paragraph 0014
(2021/02/06)
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- Replacing halogenated solvents by a butyl acetate solution of bisphenol S in the transformations of indoles
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A butyl acetate solution of bisphenol S (BPS) was proved to be able to replace hazardous halogenated solvents in the transformation of indoles. Measurement with Kamlet-Taft solvatochromic parameters disclosed that the polarity of the BPS-containing butyl acetate was enhanced greatly. The protocol not only conferred a convenient way to minimize the use of halogenated solvents in the synthesis of indole derivatives, but also enabled successful recycling of both the butyl acetate solvent and BPS additive, strengthening the greenness of the reaction systems.
- Bai, Rongxian,Ferlin, Francesco,Gao, Feng,Gu, Yanlong,Li, Minghao,Vaccaro, Luigi
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supporting information
p. 3588 - 3594
(2021/06/06)
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- Palladium-Catalyzed Three-Component Regioselective Dehydrogenative Coupling of Indoles, 2-Methylbut-2-ene, and Carboxylic Acids
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Five-carbon (C5) structural units are the fundamental building blocks of many natural products. An unprecedented palladium-catalyzed three-component dehydrogenative cascade coupling of indoles, 2-methylbut-2-ene, and carboxylic acids has been developed. The approach enables the straightforward introduction of a C3′-bonded five-carbon structural unit with a tertiary alcohol quaternary carbon center into indoles. The protocol employs 2-methylbut-2-ene as the C5 source and is featured by a broad substrate scope, atom and step economies, and high chemo- and regioselectivies.
- Guo, Rui-Li,Jia, Qiong,Wang, Meng-Yue,Wang, Yong-Qiang,Yang, Jin-Hui,Zhang, Xing-Long,Zhao, Bao-Yin
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supporting information
p. 9574 - 9579
(2021/12/14)
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- Covalent Organic Frameworks toward Diverse Photocatalytic Aerobic Oxidations
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Photoactive two-dimensional covalent organic frameworks (2D-COFs) have become promising heterogenous photocatalysts in visible-light-driven organic transformations. Herein, a visible-light-driven selective aerobic oxidation of various small organic molecules by using 2D-COFs as the photocatalyst was developed. In this protocol, due to the remarkable photocatalytic capability of hydrazone-based 2D-COF-1 on molecular oxygen activation, a wide range of amides, quinolones, heterocyclic compounds, and sulfoxides were obtained with high efficiency and excellent functional group tolerance under very mild reaction conditions. Furthermore, benefiting from the inherent advantage of heterogenous photocatalysis, prominent sustainability and easy photocatalyst recyclability, a drug molecule (modafinil) and an oxidized mustard gas simulant (2-chloroethyl ethyl sulfoxide) were selectively and easily obtained in scale-up reactions. Mechanistic investigations were conducted using radical quenching experiments and in situ ESR spectroscopy, all corroborating the proposed role of 2D-COF-1 in photocatalytic cycle.
- Liu, Shuyang,Tian, Miao,Bu, Xiubin,Tian, Hua,Yang, Xiaobo
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supporting information
p. 7738 - 7744
(2021/05/07)
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- Design, synthesis and 3D-QSAR analysis of novel thiopyranopyrimidine derivatives as potential antitumor agents inhibiting A549 and Hela cancer cells
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Four series of thiopyranopyrimidine AZD9291 derivatives containing acrylamide structure were designed, synthesized and evaluated for their antiproliferative activity against A549 and Hela cancer cells. Most of the compounds exhibited excellent antiproliferative activity against A549 cells. Moreover, the compounds with indole ring fluorine substituted exhibited better antiproliferative activity against Hela cells. The most promising compound 23g exhibited excellent enzymatic inhibitory activity and selectivity for EGFRL858R/T790M double mutations. The IC50 value against EGFRL858R/T790M kinase was 16 nM. The compound 23g inhibits selectively against the mutated form of EGFR, with the selectivity more than 125-fold. Furthermore, compound 23g also inhibited A549 cells, Hela cells and H1975 cells proliferation at a low concentration, and the IC50 values were 0.057 μM, 0.104 μM and 0.916 μM, respectively. To further investigate the QSARs of thiopyranopyrimidine derivatives, the CoMFA (q [2] = 0.765, r2 = 0.965) and CoMSIA (q [2] = 0.875, r2 = 0.956) models on Hela cancer cells were established. The generated 3D-QSAR model was validated to be reliable and can be used for further design and optimization of novel and selective EGFR inhibitors.
- Zhao, Bingbing,Zhao, Chengwu,Hu, Xiaohan,Xu, Shan,Lan, Zhou,Guo, Yuping,Yang, Zunhua,Zhu, Wufu,Zheng, Pengwu
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- Ascorbic Acid as an Aryl Radical Inducer in the Gold-Mediated Arylation of Indoles with Aryldiazonium Chlorides
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In recent years interest in the development of protocols that facilitate the oxidative addition of gold to access mild cross-coupling processes mediated by this metal has increased. In this context, we report herein that ascorbic acid, a natural and readily accessible antioxidant, can be used to accelerate the oxidative addition of aryldiazonium chlorides onto AuI. The aryl–AuIII species generated in this way, has been used to prepare 3-arylindoles in a one-pot protocol starting from anilines and para-, meta-, and ortho- substituted aryldiazonium chlorides. The mechanism underlying the oxidative addition has been examined in detail based on EPR analyses, cyclic voltammetry, and DFT calculations. Interestingly, we have found that in this protocol, the chloride atom induces the AuII/AuIII oxidation step.
- Medina-Mercado, Ignacio,Asomoza-Solís, Eric Omar,Martínez-González, Eduardo,Ugalde-Saldívar, Victor Manuel,Ledesma-Olvera, Lydia Gabriela,Barquera-Lozada, José Enrique,Gómez-Vidales, Virginia,Barroso-Flores, Joaquín,Frontana-Uribe, Bernardo A.,Porcel, Susana
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supporting information
p. 634 - 642
(2019/12/11)
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- Isothiourea-Catalyzed Enantioselective Synthesis of Tetrahydro-α-carbolinones
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An isothiourea-catalyzed enantioselective annulation protocol using indolin-2-imines with a series of α,β-unsaturated p-nitrophenyl esters for the synthesis of tetrahydro-α-carbolinones was developed. Using 5 mol % of the isothiourea HyperBTM as the Lewis base catalyst, this process allows the enantioselective preparation of a range of C(4)-substituted tetrahydro-α-carbolinones in good to excellent yield and with high enantioselectivity (20 examples, 32-99% yield and up to 99:1 er).
- Liu, Honglei,Slawin, Alexandra M. Z.,Smith, Andrew D.
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supporting information
p. 1301 - 1305
(2020/02/25)
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- Tridentate Nickel(II)-Catalyzed Chemodivergent C-H Functionalization and Cyclopropanation: Regioselective and Diastereoselective Access to Substituted Aromatic Heterocycles
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A Schiff-base nickel(II)-phosphene-catalyzed chemodivergent C-H functionalization and cyclopropanation of aromatic heterocycles is reported in moderate to excellent yields and very good regioselectivity and diastereoselectivity. The weak, noncovalent interaction between the phosphene ligand and Ni center facilitates the ligand dissociation, generating the electronically and coordinatively unsaturated active catalyst. The proposed mechanisms for the reported reactions are in good accord with the experimental results and theoretical calculations, providing a suitable model of stereocontrol for the cyclopropanation reaction.
- Nag, Ekta,Gorantla, Sai Manoj N. V. T.,Arumugam, Selvakumar,Kulkarni, Aditya,Mondal, Kartik Chandra,Roy, Sudipta
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supporting information
p. 6313 - 6318
(2020/09/02)
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- Exploring the Labile Nature of 2,4,6-Trimethoxyphenyl Moiety in Allylic Systems under Acidic Conditions
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An investigation of the unexpected lability of the Csp3–Csp2 bond connecting 2,4,6-trimethoxyphenyl group and an allylic moiety is carried out. We observed that the catalytic presence of either Lewis or Br?nsted acid can render such 2,4,6-trimethoxyphenyl group labile. Several nucleophiles were found to substitute the labile C–C bond in mild reaction conditions resulting in very good yields of the allylated products. Even in the absence of a nucleophile, intramolecular cyclization of the parent substrate under acidic activation caused the labile C–C bond to cleave. A major motivation of this study is to understand the lability of electron-rich aryl group in acidic medium, employing 2,4,6-trimethoxyphenyl moiety as a case study. A plausible mechanism is proposed after carrying out several control reactions as well as UV/Vis and 1H NMR spectroscopic studies. This work provides an insight into the activation of electron-rich arenes as a labile entity in acidic medium while also adding a conceptually novel C–C bond breaking approach to the vast literature of allylation of arenes.
- Paul, Dipankar,Chatterjee, Paresh Nath
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supporting information
p. 4705 - 4712
(2020/07/28)
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- Visible-Light-Induced, Base-Promoted Transition-Metal-Free Dehalogenation of Aryl Fluorides, Chlorides, Bromides, and Iodides
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We report a simple and efficient visible-light-induced transition-metal-free hydrogenation of aryl halides. The combined visible light and base system is used to initiate the desired radical-mediated hydrogenation. A variety of aryl fluorides, chlorides, bromides, and iodides could be reduced to the corresponding (hetero)arenes with excellent yields under mild conditions. Various functional groups and other heterocyclic compounds are tolerated.
- Ding, Ting-Hui,Qu, Jian-Ping,Kang, Yan-Biao
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p. 3084 - 3088
(2020/04/10)
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- Selective Methylation of Amides, N-Heterocycles, Thiols, and Alcohols with Tetramethylammonium Fluoride
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We herein disclose the use of tetramethylammonium fluoride (TMAF) as a direct and selective methylating agent of a variety of amides, indoles, pyrroles, imidazoles, alcohols, and thiols. The method is characterized by operational simplicity, wide scope, and ease of purification. Our computational studies suggest a concerted methylation-deprotonation as the preferred reaction pathway.
- Cheng, Hong-Gang,Pu, Maoping,Kundu, Gourab,Schoenebeck, Franziska
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supporting information
p. 331 - 334
(2019/12/30)
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- Exploiting the radical reactivity of diazaphosphinanes in hydrodehalogenations and cascade cyclizations
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The remarkable reducibility of diazaphosphinanes has been extensively applied in various hydrogenations, based on and yet limited by their well-known hydridic reactivity. Here we exploited their unprecedented radical reactivity to implement hydrodehalogenations and cascade cyclizations originally inaccessible by hydride transfer. These reactions feature a broad substrate scope, high efficiency and simplicity of manipulation. Mechanistic studies suggested a radical chain process in which a phosphinyl radical is generated in a catalytic cycle via hydrogen-atom transfer from diazaphosphinanes. The radical reactivity of diazaphosphinanes disclosed here differs from their well-established hydridic reactivity, and hence, opens a new avenue for diazaphosphinane applications in organic syntheses.
- Cheng, Jin-Pei,Yang, Jin-Dong,Zhang, Jingjing
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p. 4786 - 4790
(2020/06/18)
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- Aerobic Dehydrogenation of N-Heterocycles with Grubbs Catalyst: Its Application to Assisted-Tandem Catalysis to Construct N-Containing Fused Heteroarenes
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An aerobic dehydrogenation of nitrogen-containing heterocycles catalyzed by Grubbs catalyst is developed. The reaction is applicable to various nitrogen-containing heterocycles. The exceptionally high functional group compatibility of this method was confirmed by the oxidation of an unprotected dihydroindolactam V to indolactam V. Furthermore, by taking advantage of the oxygen-mediated structural change of the Grubbs catalyst, we integrated ring-closing metathesis and subsequent aerobic dehydrogenation to develop the novel assisted-tandem catalysis using molecular oxygen as a chemical trigger. The utility of the assisted-tandem catalysis was demonstrated by the concise synthesis of N-containing fused heteroarenes including a natural antibiotic, pyocyanine.
- Kawauchi, Daichi,Noda, Kenta,Komatsu, Yoshiyuki,Yoshida, Kei,Ueda, Hirofumi,Tokuyama, Hidetoshi
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p. 15793 - 15798
(2020/10/12)
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- Copper-mediated rapid and facile oxidative dehydrogenation of dihydrobenzocarbazoles
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Rapid method for the oxidative dehydrogenation of dihydrobenzocarbazoles has been introduced by using bench scale and commercially available reagent; copper chloride, in excellent yield with easy workup. The scope of the reaction has been studied with broad range of substitutes.
- Humne, Vivek T.,Ulhe, Avinash G.
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supporting information
(2020/03/16)
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- γ-Carboline synthesis enabled by Rh(iii)-catalysed regioselective C-H annulation
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A redox-neutral Rh(iii)-catalyzed C-H annulation of indolyl oximes was developed. Relying on the use of various alkynyl silanes as the terminal alkyne surrogates, the reaction exhibited a reverse regioselectivity, thus giving an exclusive and easy way for the synthesis of a wide range of substituent free γ-carbolines at C3 position with high efficiency. Deuterium-labelling experiments and kinetic analysis have preliminarily shed light on the working mode of this catalytic system. This journal is
- Jiang, Bo,Jia, Jingwen,Sun, Yufei,Wang, Yichun,Zeng, Jing,Bu, Xiubin,Shi, Liangliang,Sun, Xiaoying,Yang, Xiaobo
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supporting information
p. 13389 - 13392
(2020/11/10)
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- The palladium-catalyzed direct C3-cyanation of indoles using acetonitrile as the cyanide source
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The ligand-free palladium-catalyzed C3-cyanation of indoles via direct C-H functionalization was achieved. This protocol, utilizing CH3CN as a green and readily available cyanide source, produced the desired products in moderate to good yields through transition-metal-catalyzed C-CN bond cleavage. This journal is
- Feng, Kejun,Li, Qiang,Li, Yuanhua,Liu, Bifu,Liu, Min,Zhou, Yongbo
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supporting information
p. 6108 - 6114
(2020/10/21)
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- A rhodium(ii) catalysed domino synthesis of azepino fused diindoles from isatin tethered: N -sulfonyl-1,2,3-triazoles and indoles
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An efficient and convenient protocol for the synthesis of a novel class of azepino fused diindoles from isatin tethered N-sulfonyl-1,2,3-triazoles and indoles has been disclosed. The reaction proceeds via denitrogenative aza-vinyl rhodium carbene formation to give a carbonyl ylide, which with indole results in 1,3-dipolar cycloaddition followed by sequential semipinacol rearrangement/ring expansion/oxidation to produce azepino fused diindoles. The reaction shows a broad substrate scope giving up to 81% yield. Furthermore, reversible catalytic hydrogenation and photophysical studies were carried out to demonstrate the application of these molecules.
- Kahar, Nilesh,Jadhav, Pankaj,Reddy, R. V. Ramana,Dawande, Sudam
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supporting information
p. 1207 - 1210
(2020/02/04)
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- Cobalt-Catalyzed Cycloamination: Synthesis and Photophysical Properties of Polycyclic N-Heterocycles
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The first earth-abundant cobalt-catalyzed cycloamination of indolylquinones and various (hetero)aromatic amine under ligand-free conditions for the synthesis of polycyclic N-heterocycles has been developed. The process allows facile access to polycyclic N-heterocycles with tolerance of chloride, bromide, amino, thio, etc. groups in moderate to high yields (up to 89percent). In addition, The photophysical properties of the synthesized products were evaluated. These products exhibit interesting fluorescence properties, which is promising for fluorescent probes.
- Dong, Yu,He, Shuai,Shi, Zhi-Chuan,Wang, Ji-Yu,Yang, Jian,Zhan, Xiao-Yu,Zhang, Hua,Zhang, Xiao-Mei
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supporting information
(2020/07/15)
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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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- Catalytic Aerobic Dehydrogenatin of N-Heterocycles by N-Hydoxyphthalimide
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Catalytic methods for the aerobic dehydrogenation of N-heterocycles are reported. In most cases, indoles are accessed efficiently from indolines using catalytic N-hydroxyphthalimide (NHPI) as the sole additive under air. Further studies revealed an improved catalytic system of NHPI and copper for the preparation of other heteroaromatics, for example quinolines. (Figure presented.).
- Chen, Weidong,Tang, Hao,Wang, Weilin,Fu, Qiang,Luo, Junfei
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supporting information
p. 3905 - 3911
(2020/08/10)
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- Method for preparing indole compound through air oxidation catalyzed by N-hydroxyphthalimide
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The invention discloses a method for preparing an indole compound through non-transition metal catalyzed air oxidation. According to the method, the low-cost N-hydroxyphthalimide is used as a catalystand air is used as an oxidizing agent, wherein indoline compounds are oxidized in an organic solvent, and synthesis of the indoline compounds is achieved. The method has the advantages of simple reaction operation, low reaction cost, high yield, mild conditions, no heavy metal pollution and the like.
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Paragraph 0031-0037
(2020/11/23)
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- A Visible-Light Promoted Amine Oxidation Catalyzed by a Cp*Ir Complex
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Through a rapid screening of Cp*Ir complexes based on a turn-on type fluorescence readout, a [Cp*Ir(dipyrido[3,2-a : 2’,3’-c]phenazine)Cl]+ complex was found to catalyze the blue-light promoted dehydrogenation of N-heterocycles under physiological conditions. In the dehydrogenation of tetrahydroisoquinolines, the catalyst preferentially yielded the monodehydrogenated product, accompanying H2O2 generation. We surmise that this mechanism may be reminiscent of flavin-dependent oxidases.
- Davis, Holly Jane,H?ussinger, Daniel,Ward, Thomas R.,Okamoto, Yasunori
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p. 4512 - 4516
(2020/07/27)
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- Synthesis of 2-substituted indoles through cyclization and demethylation of 2-alkynyldimethylanilines by ethanol
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Herein, we demonstrated that 2-alkynyldimethylamines easily cyclize in EtOH according to a 5-endo-dig annulation into 2-substituted indoles without the aid of any additives or any metal catalysts to activate the triple bond. Thus, a variety of functionalized 2-styrylindoles, 2-arylindoles, 2-alkynylindoles, and 2-alkylindoles were prepared in high to excellent yields according to an environmentally friendly protocol. The mechanism has been explored to better understand this eco-friendly access to 2-substituted indoles and DFT calculations rationalized the role of the solvent in this N-annulation/dealkylation process.
- Zhao, Guangkuan,Roudaut, Christelle,Gandon, Vincent,Alami, Mouad,Provot, Olivier
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supporting information
p. 4204 - 4210
(2019/08/07)
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- Highly-chemoselective step-down reduction of carboxylic acids to aromatic hydrocarbons: Via palladium catalysis
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Aryl carboxylic acids are among the most abundant substrates in chemical synthesis and represent a perfect example of a traceless directing group that is central to many processes in the preparation of pharmaceuticals, natural products and polymers. Herein, we describe a highly selective method for the direct step-down reduction of carboxylic acids to arenes, proceeding via well-defined Pd(0)/(ii) catalytic cycle. The method shows a remarkably broad substrate scope, enabling to direct the classical acyl reduction towards selective decarbonylation by a redox-neutral mechanism. The utility of this reaction is highlighted in the direct defunctionalization of pharmaceuticals and natural products, and further emphasized in a range of traceless processes using removable carboxylic acids under mild, redox-neutral conditions orthogonal to protodecarboxylation. Extensive DFT computations were conducted to demonstrate preferred selectivity for the reversible oxidative addition and indicated that a versatile hydrogen atom transfer (HAT) pathway is operable.
- Liu, Chengwei,Qin, Zhi-Xin,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
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p. 5736 - 5742
(2019/06/18)
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- Catalyst-free assembly of giant tris(heteroaryl)methanes: Synthesis of novel pharmacophoric triads and model sterically crowded tris(heteroaryl/aryl)methyl cation salts
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A series of giant tris(heteroaryl)methanes are easily assembled by one-pot three-component synthesis by simple reflux in ethanol without catalyst or additives. Diversely substituted indoles (Ar1) react with quinoline aldehydes, quinolone aldehydes, chromone aldehydes, and fluorene aldehydes (Ar2CHO) and coumarins (Ar3) in 1:1:1 ratio to form the corresponding tris(heteroaryl)methanes (Ar1Ar2Ar3)CH along with (Ar1Ar1Ar2)CH triads. A series of new 2:1 triads were also synthesized by coupling substituted indoles with Ar2CHO. The coupling reactions could also be carried out in water (at circa 80 °C) but with chemoselectivity favoring (Ar1Ar1Ar2)CH(Ar1Ar2Ar3)CH. The molecular structure of a representative (Ar1Ar2Ar3)CH triad was confirmed by X-ray analysis. Model tris(heteroaryl/aryl)methylium salts were generated by reaction with DDQ/HPF6 and studied by NMR and by DFT and GIAO-DFT.
- Abonia, Rodrigo,Gutiérrez, Luisa F.,Insuasty, Braulio,Quiroga, Jairo,Laali, Kenneth K.,Zhao, Chunqing,Borosky, Gabriela L.,Horwitz, Samantha M.,Bunge, Scott D.
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p. 642 - 654
(2019/04/17)
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- Competing dehalogenation versus borylation of aryl iodides and bromides under transition-metal-free basic conditions
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In this work, selectivity-controllable base-promoted transition-metal-free borylation and dehalogenation of aryl halides are described. Under the conditions of borylation, the dehalogenation which emerges as a competitive side reaction has been well-controlled by carefully controlling the borylation conditions. On the other hand, the dehalogenation using benzaldehyde as a hydrogen source has also been accomplished. The applications of direct radical borylation and dehalogenation of aryl halides demonstrate their synthetic practicability in pharmaceutical-oriented organic synthesis. Based on the experimental evidences, the tBuOK/1,10-Phen-triggered radical nature of both competitive reactions has been revealed.
- Niu, Yi-Jie,Sui, Guo-Hui,Zheng, Hong-Xing,Shan, Xiang-Huan,Tie, Lin,Fu, Jia-Le,Qu, Jian-Ping,Kang, Yan-Biao
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p. 10805 - 10813
(2019/09/30)
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- A phenyl acrylamide structure containing substituted pyrimidine compound and use thereof (by machine translation)
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The invention discloses a containing substituted phenyl acrylamide structure of the pyridine compound, its geometric isomer and its pharmaceutically acceptable salt, hydrate, solvate or prodrug. The invention containing substituted phenyl acrylamide structure of pyrimidines, and its pharmaceutically acceptable salt, hydrate or solvate thereof as an active ingredient, with a pharmaceutically acceptable carrier or excipient mixed preparation composition in, and prepared into a clinically acceptable dosage form. The compounds of the invention in preparing and treating and/or preventing proliferative disorders application of the medicament, for treating and/or preventing cancer of application of the medicament, for treating and/or preventing lung cancer, prostate cancer, breast cancer and applied in the medicine of cervical cancer. (by machine translation)
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Paragraph 0054; 0083; 0084
(2019/02/10)
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- Metal-free synthesis of benzimidazo[1,2-c]quinazolin-6-ones with indole and benzenediamine oxidized by I2/TBHP
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A variety of benzimidazo[1,2-c]quinazolin-6-ones derivatives can be accessed in moderate to good yields under simple and metal-free reaction conditions using indoles and o-benzenediamines oxidized by iodine and TBHP. This procedure works in reasonable yields for different indoles as well as o-benzenediamines thus may provide a good synthesis of quinazolinones. A TBHP oxidized ring expansion reaction mechanism that explains the synthesis of benzimidazo[1,2-c]quinazolin-6-ones were reported.
- Dai, Zhen,Li, Songhua,Li, Yunyi,Feng, Lei,Ma, Chen
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supporting information
p. 2012 - 2017
(2019/02/20)
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- Electrochemical Regioselective Bromination of Electron-Rich Aromatic Rings Using n Bu 4 NBr
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Electrochemical regioselective bromination of electron-rich aromatic rings using stoichiometric tetrabutylammonium bromide (n Bu 4 NBr) has been accomplished under mild conditions. This protocol provides an environmentally friendly and simple way for the construction of C-Br bond in moderate to high yields with wide functional group tolerance.
- Bai, Ya,Che, Xin,Liu, Nian,Ning, Shulin,Shi, Lingling,Wang, Shutao,Wang, Siyu,Xiang, Jinbao,Xie, Wenxia
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supporting information
p. 1313 - 1316
(2019/06/20)
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- Method for continuously preparing 3,4-(1-methyl-indol-3-yl)-1H-pyrrole-2,5-one compound by microchannel reactor
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The invention discloses a method for continuously preparing a 3,4-(1-methyl-indol-3-yl)-1H-pyrrole-2,5-one compound by a microchannel reactor. The method comprises the following steps: dissolving 1-methyl-3-indole acetamide and 1-methyl indolo ketonic acid methyl ester into anhydrous dimethylformamide (DMF) to form a mixed solution which is a solution A; dissolving potassium tert-butoxide in anhydrous DMF, and uniformly carrying out mixing to obtain a solution B; and feeding the prepared solution A and the prepared solution B into the microchannel reactor for a reaction, enabling a reacted material liquid to flow out from an outlet of the microchannel reactor after the reaction process is finished, and carrying out post-treatment on the reacted material liquid to obtain the 3,4-(1-methyl-indol-3-yl)-1H-pyrrole-2,5-one compound. According to the method disclosed by the invention, the 3,4-(1-methyl-indol-3-yl)-1H-pyrrole-2,5-one is continuously prepared through the microchannel reactor,and the method has the advantages of mild conditions, high reaction speed, high yield, suitability for industrial production, and the like.
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Paragraph 0028; 0032-0034
(2019/05/15)
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- Tandem Rh(III)-Catalyzed C-H Heteroarylation of Indolyl Ketones and Cu(II)-Promoted Intramolecular Cyclization: One-Pot Access to Blue-Emitting Phenanthrone-Type Polyheterocycles
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Disclosed herein is a highly efficient one-pot synthetic strategy to phenanthrone-type polyheterocycles via tandem rhodium(III)-catalyzed ortho-C-H heteroarylation of indolyl ketones and copper(II)-promoted intramolecular cyclization. This protocol enables a library of blue-emitting fluorophores with high quantum yields and narrow full widths at half-maximum to be rapidly built from readily available substrates, among of which 6,6,7,9,12-pentamethyl-6,12-dihydro-5H-benzofuro[2,3-a]carbazol-5-one (4a) exhibits pure blue emission with Commission Internationale de I'Eclairage coordinates of (0.15, 0.09) and a high quantum yield of 85% in CH2Cl2 solution.
- Pu, Xingwen,Zhang, Mangang,Lan, Jingbo,Chen, Shuyou,Liu, Zheng,Liang, Wenbo,Yang, Yudong,Zhang, Min,You, Jingsong
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supporting information
p. 1139 - 1143
(2019/05/16)
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- Synthesis of 3-Formylindoles via Electrochemical Decarboxylation of Glyoxylic Acid with an Amine as a Dual Function Organocatalyst
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A new method for 3-formalytion of indoles has been developed through electrochemical decarboxylation of glyoxylic acid with the amine as a dual function organocatalyst. The amine facilitated both the electrochemical decarboxylation and the nucleophilic reaction efficiently, whose loading can be as low as 1 mol %. This protocol has a broad range of functional group tolerance under ambient conditions. The gram-scale experiment has shown great potential in the synthetic application of this strategy.
- Lin, Dian-Zhao,Huang, Jing-Mei
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supporting information
p. 5862 - 5866
(2019/08/26)
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- Design, synthesis and biological evaluation of AZD9291 derivatives as selective and potent EGFRL858R/T790M inhibitors
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Third-generation epidermal growth factor receptor (EGFR)L858R/T790M inhibitors are still the main drugs for the treatment of advanced non-small cell lung cancer (NSCLC), and these drugs have achieved remarkable clinical efficacy. However, there are still many patients suffering from drug-resistant mutations and drug side effects caused by NSCLC. In this study, guided by the molecular simulation, we applied a structure-based drug design strategy (SBDD) and optimized the structure to obtain a series of potent and selective EGFRL858R/T790M inhibitors. The most potent compound 18e demonstrated excellent kinase inhibitory activity and selectivity for EGFRL858R/T790M double mutants and the IC50 value reached nanomolar level. The selectivity of 18e against wild-type EGFR was near to 200-fold. In addition, compound 18e also inhibited H1975 cells proliferation at G2/M phase and induced apoptosis at a concentration of 0.25 μM, which makes it more valuable for potential lung cancer research.
- Zhao, Bingbing,Xiao, Zhen,Qi, Jianguo,Luo, Rong,Lan, Zhou,Zhang, Yanzhuo,Hu, Xiaohan,Tang, Qidong,Zheng, Pengwu,Xu, Shan,Zhu, Wufu
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p. 367 - 380
(2018/12/13)
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- Tryptamine derivatives disarm colistin resistance in polymyxin-resistant gram-negative bacteria
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The last three decades have seen a dwindling number of novel antibiotic classes approved for clinical use and a concurrent increase in levels of antibiotic resistance, necessitating alternative methods to combat the rise of multi-drug resistant bacteria. A promising strategy employs antibiotic adjuvants, non-toxic molecules that disarm antibiotic resistance. When co-dosed with antibiotics, these compounds restore antibiotic efficacy in drug-resistant strains. Herein we identify derivatives of tryptamine, a ubiquitous biochemical scaffold containing an indole ring system, capable of disarming colistin resistance in the Gram-negative bacterial pathogens Acinetobacter baumannii, Klebsiella pneumoniae, and Escherichia coli while having no inherent bacterial toxicity. Resistance was overcome in strains carrying endogenous chromosomally-encoded colistin resistance machinery, as well as resistance conferred by the mobile colistin resistance-1 (mcr-1) plasmid-borne gene. These compounds restore a colistin minimum inhibitory concentration (MIC) below the Clinical & Laboratory Sciences Institute (CLSI) breakpoint in all resistant strains.
- Barker, William T.,Chandler, Courtney E.,Melander, Roberta J.,Ernst, Robert K.,Melander, Christian
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p. 1776 - 1788
(2019/03/21)
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