- The Marriage of Carborane with Chalcogen Atoms: Nonconjugation, σ-πConjugation, and Intramolecular Charge Transfer
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A series of chalcogen-containing carborane derivatives were synthesized through a one-pot reaction. The nonconjugated six-membered ring of carborane-fused disulfide (1) can be electrochemically reduced to a dithiolate derivative. The five-membered ring of carborane-fused chalcogenophenes (2-4) showed aromaticity and considerable σ-πconjugation. The dicarborane chalcogenides (5-7) showed intramolecular charge-transfer-induced emission. These chalcogen-containing carborane derivatives provided a useful platform to study the electron interaction systematically and shed some light on the design of carborane-based optoelectronic materials.
- Yang, Xiaodong,Zhang, Bingjie,Zhang, Sikun,Li, Guoping,Xu, Letian,Wang, Zhijun,Li, Pengfei,Zhang, Yanfeng,Liu, Zishun,He, Gang
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Read Online
- Electrochemical Iodoamination of Indoles Using Unactivated Amines
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An environmentally friendly electrochemical approach for iodoamination of various indole derivatives with a series of unactivated amines, amino acid derivatives, and benzotriazoles (more than 80 examples) has been developed. This strategy was further applied in late-stage functionalization of natural products and pharmaceuticals and gram-scale synthesis and radiosynthesis of 131I-labeled compounds. Fundamental insights into the mechanism of the reaction based on control experiments, density functional theory calculation, and cyclic voltammetry are provided.
- Lei, Ning,Shen, Yanling,Li, Yujun,Tao, Pan,Yang, Liquan,Su, Zhishan,Zheng, Ke
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Read Online
- Design of an Electron-Withdrawing Benzonitrile Ligand for Ni-Catalyzed Cross-Coupling Involving Tertiary Nucleophiles
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The design of new ligands for cross-coupling is essential for developing new catalytic reactions that access valuable products such as pharmaceuticals. In this report, we exploit the reactivity of nitrile-containing additives in Ni catalysis to design a benzonitrile-containing ligand for cross-coupling involving tertiary nucleophiles. Kinetic and Hammett studies are used to elucidate the role of the optimized ligand, which demonstrate that the benzonitrile moiety acts as an electron-acceptor to promote reductive elimination over β-hydride elimination and stabilize low-valent Ni. With these conditions, a protocol for decyanation-metalation and Ni-catalyzed arylation is conducted, enabling access to quaternary α-arylnitriles from disubstituted malononitriles.
- Edjoc, Racquel K.,Mills, L. Reginald,Rousseaux, Sophie A. L.
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p. 10422 - 10428
(2021/07/26)
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- PIKFYVE KINASE INHIBITORS
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The present invention relates to compounds useful as inhibitors of phosphatidylinositol-3-phosphate 5-kinase (PIKfyve) as well as their use for treating diseases and disorders associated with PIKfyve.
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- Short Synthesis of Oxetane and Azetidine 3-Aryl-3-carboxylic Acid Derivatives by Selective Furan Oxidative Cleavage
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Four-membered rings remain underexplored motifs despite offering attractive physicochemical properties for medicinal chemistry. Arylacetic acids bearing oxetanes, azetidines, and cyclobutanes are prepared in two steps: a catalytic Friedel-Crafts reaction from four-membered ring alcohol substrates, followed by mild oxidative cleavage. The suitability of the products as building blocks is reflected in their facile purification and amenability to derivatization. Examples include heteroaromatics and aryltriflates, as well as oxetane-derived profen drug analogues and a new endomorphin derivative containing an azetidine amino acid residue.
- Bull, James A.,Choi, Chulho,Dubois, Maryne A. J.,Lee Wei Jie, Alvin,Mousseau, James J.,Smith, Milo A.,White, Andrew J. P.
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supporting information
p. 5279 - 5283
(2020/08/14)
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- Mechanistic and experimental study on copper-catalyzed C3-sulfenylation of indoles with sulfur powder and aryl iodides
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The copper-catalyzed sulfenylation of indoles with aryl iodide and sulfur powder has been investigated both experimentally and theoretically. This protocol provides a direct and facile approach to prepare 3-sulfenylindoles with moderate to excellent yields and good functional-group tolerance. The in-situ IR analysis provided evidence for that NaOAc could promote the synthesis of diphenyl disulfide by the coupling of aryl iodide and sulfur powder. According to DFT calculations, the coupling pathway involving the intermediate N-methyl-3-iodoindole is more favored than the direct coupling by the C–H activation of indole. The N-methyl-3-iodoindole was identified as a crucial intermediate in the catalytic cycle.
- Ge, Xin,Cheng, Lin,Sun, Fengli,Liu, Xuemin,Chen, Xinzhi,Qian, Chao,Zhou, Shaodong
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- Direct electrosynthesis for: N-alkyl-C3-halo-indoles using alkyl halide as both alkylating and halogenating building blocks
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An electrochemically induced tandem reaction has been developed for selective N1-alkylation and C3-halogenation of indoles. This electrochemical difunctionalization strategy circumvents conventional multi-step procedures and efficiently generates syntheti
- Sun, Linhao,Zhang, Xing,Wang, Chenguang,Teng, Huailong,Ma, Jimei,Li, Zilong,Chen, Hao,Jiang, Hong
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supporting information
p. 2732 - 2738
(2019/06/13)
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- Systematic Evaluation of Sulfoxides as Catalysts in Nucleophilic Substitutions of Alcohols
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Herein, a method for the nucleophilic substitution (SN) of benzyl alcohols yielding chloro alkanes is introduced that relies on aromatic sulfoxides as Lewis base catalysts (down to 1.5 mol-%) and benzoyl chloride (BzCl) as reagent. A systematic screening of various sulfoxides and other sulfinyl containing Lewis bases afforded (2-methoxyphenyl)methyl sulfoxide as optimal catalyst. In contrast to reported formamide catalysts, sulfoxides also enable the application of plain acetyl chloride (AcCl) as reagent. In addition, it was demonstrated that weakly electrophilic carboxylic acid chlorides like BzCl promote Pummerer rearrangement of sulfoxides already at room temperature. This side-reaction also provided the explanation, why sulfoxide catalyzed SN-reactions of alcohols do not allow the effective production of aliphatic and electron deficient chloro alkanes. Comparison experiments provided further insight into the reaction mechanism.
- Motsch, Sebastian,Schütz, Christian,Huy, Peter H.
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supporting information
p. 4541 - 4547
(2018/09/13)
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- PhI(OAc)2/NaX-mediated halogenation providing access to valuable synthons 3-haloindole derivatives
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This paper describes a mild phenyliodine diacetate mediated method for selective chlorination, bromination, and iodination of indole C-H bonds using sodium halide as a source for analogous halogenations. The combination of NaX and phenyliodine diacetate provides an invincible system for halogenation of indoles. This protocol was compatible with a wide array of indole substrates and provides straight forward access to potential halogenated arenes.
- Himabindu, Vittam,Parvathaneni, Sai Prathima,Rao, Vaidya Jayathirtha
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p. 18889 - 18893
(2018/11/27)
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- Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings
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Constructing products of high synthetic value from inexpensive and abundant starting materials is of great importance. Aryl iodides are essential building blocks for the synthesis of functional molecules, and efficient methods for their synthesis from chemical feedstocks are highly sought after. Here we report a low-cost decarboxylative iodination that occurs simply from readily available benzoic acids and I2. The reaction is scalable and the scope and robustness of the reaction is thoroughly examined. Mechanistic studies suggest that this reaction does not proceed via a radical mechanism, which is in contrast to classical Hunsdiecker-type decarboxylative halogenations. In addition, DFT studies allow comparisons to be made between our procedure and current transition-metal-catalyzed decarboxylations. The utility of this procedure is demonstrated in its application to oxidative cross-couplings of aromatics via decarboxylative/C-H or double decarboxylative activations that use I2 as the terminal oxidant. This strategy allows the preparation of biaryls previously inaccessible via decarboxylative methods and holds other advantages over existing decarboxylative oxidative couplings, as stoichiometric transition metals are avoided.
- Perry, Gregory J. P.,Quibell, Jacob M.,Panigrahi, Adyasha,Larrosa, Igor
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supporting information
p. 11527 - 11536
(2017/08/30)
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- Tyrosine Kinase Inhibitor And Uses Thereof
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Disclosed is a compound of Formula (I) or a pharmaceutically acceptable salt, ester, or solvate thereof, or their stereoisomers, which can be used as tyrosine kinase inhibitor. Also disclosed is a method for preparing the compound, a pharmaceutical composition and a kit comprising the compound, and uses of the compound. The compound can be used as tyrosine kinase inhibitor, or can be used to reduce or inhibit activity of EGFR or mutant thereof, such as EGFR mutant comprising T790M mutation, in a cell, or to treat and/or prevent a disease associated with overactivity of EGFR, such as cancer.
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- Acylation of indoles via photoredox catalysis: A route to 3-acylindoles
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A visible-light-induced synthesis of 3-acylindoles from simple indoles and α-oxo acids at room temperature has been discovered. The reaction tolerates a wide range of functional groups and gives a variety of valuable 3-acylindoles in moderate to high yields under mild conditions.
- Gu, Lijun,Jin, Cheng,Liu, Jiyan,Zhang, Hongtao,Yuan, Minglong,Li, Ganpeng
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p. 1201 - 1205
(2016/03/09)
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- Decarboxylative Halogenation and Cyanation of Electron-Deficient Aryl Carboxylic Acids via Cu Mediator as Well as Electron-Rich Ones through Pd Catalyst under Aerobic Conditions
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Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (-I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX (X = I, Br, Cl), and easy preparation of benzonitriles from decarboxylative cyanation of aryl carboxylic acids with nontoxic and low-cost K4Fe(CN)6 under an oxygen atmosphere for the first time.
- Fu, Zhengjiang,Li, Zhaojie,Song, Yuanyuan,Yang, Ruchun,Liu, Yanzhu,Cai, Hu
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p. 2794 - 2803
(2016/04/26)
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- Palladium-catalyzed carbonylation of indoles for synthesis of indol-3-yl aryl ketones
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A novel palladium-catalyzed carbonylation of indoles with CO and aromatic boronic acids for the synthesis of indol-3-yl aryl ketones was developed. The reaction tolerates a wide range of functional groups and gives a variety of valuable indol-3-yl aryl ketones in high yields under mild conditions. (Chemical Presented).
- Zhao, Mi-Na,Ran, Longfei,Chen, Ming,Ren, Zhi-Hui,Wang, Yao-Yu,Guan, Zheng-Hui
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p. 1210 - 1213
(2015/02/19)
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- Copper-mediated selective aerobic oxidative C3-cyanation of indoles with DMF
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Under an oxygen atmosphere, the copper-mediated direct C3-cyanation of indole C-H bonds, using cheap and safe DMF as a CN source, took place selectively to produce the corresponding C3-cyanoindoles in good yields. A possible mechanism for this selective cyanation was proposed.
- Xiao, Jing,Li, Qiang,Chen, Tieqiao,Han, Li-Biao
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supporting information
p. 5937 - 5940
(2015/11/02)
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- Iodine-catalyzed oxidative cross-coupling of indoles and azoles: Regioselective synthesis of N -linked 2-(Azol-1-yl)indole derivatives
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A highly efficient iodine-catalyzed regioselective oxidative cross-coupling of an indole C-H bond and azole N-H bond is described. This metal-free reaction can be easily carried out at room temperature under mild and environmentally friendly conditions and provides a series of N-linked 2-(azol-1-yl)indole derivatives in moderate to excellence yields.
- Beukeaw, Danupat,Udomsasporn, Kwanchanok,Yotphan, Sirilata
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supporting information
p. 3447 - 3454
(2015/04/14)
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- Cyanine-like dyes with large bond-length alternation
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Herein, the synthesis and properties of alkyne-bridged carbocations, which are analogous in structure to cyanine dyes, are reported. An alkene-bridged dye, linked at the third position of the indole, was also synthesized as a reference compound. These new carbocations are stable under ambient conditions, allowing characterization by UV/Vis and NMR (1H and 13C) spectroscopies. These techniques revealed a large degree of delocalization of the positive charge, similar to a previously reported porphyrin carbocation. The linear and nonlinear optical properties are compared with cyanine dyes and triarylmethyl cations, to investigate the effects of the bond-length alternation and the overall molecular geometry. The value of Re(γ), the real part of the third-order microscopic polarizability, of -1.3×10-33 esu for the alkyne-linked cation is comparable to that of a cyanine dye of similar length. Nondegenerate two-photon absorption spectra showed that the alkene-bridged dye exhibited characteristics of cyanines, whereas the alkyne-bridged dye is reminiscent of octupolar chromophores, such as the triarylmethyl carbocation brilliant green. Such attributes were confirmed and rationalized by quantum chemical calculations. Copyright
- Thorley, Karl J.,Hales, Joel M.,Kim, Hyeongeu,Ohira, Shino,Bredas, Jean-Luc,Perry, Joseph W.,Anderson, Harry L.
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p. 10370 - 10377
(2013/09/02)
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- Nonnatural amino acid synthesis by using carbon-hydrogen bond functionalization methodology
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Taking direction well: Substituted phenylalanine derivatives were prepared by C-H bond functionalization (see scheme). The syntheses are highly convergent and employ an N-phthaloylalanine with a 2-thiomethylaniline directing group. The use of an 8-aminoquinoline directing group allows for the diarylation of methyl and the diastereoselective arylation of methylene groups. Copyright
- Tran, Ly Dieu,Daugulis, Olafs
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supporting information; experimental part
p. 5188 - 5191
(2012/07/27)
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- Copper-catalysed direct C-H bond oxidative acetoxylation and iodination of indoles
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A novel Cu(OAc)2-catalysed direct C-H bond oxidative acetoxylation and iodination of indoles using PhI(OAc)2 as a terminal oxidant is reported. Adopting this method, a series of 3-iodoindoles and indol-3-yl acetates were obtained in nearly 1:1 ratio yield.
- Ge, Shao-Peng,Zhang, Xiao-Hong,Han, Jiang-Sheng,Zhong, Ping
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experimental part
p. 356 - 359
(2012/10/08)
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- Formal homo-nazarov and other cyclization reactions of activated cyclopropanes
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The Nazarov cyclization of divinyl ketones gives access to cyclopentenones. Replacing one of the vinyl groups by a cyclopropane leads to a formal homo-Nazarov process for the synthesis of cyclohexenones. In contrast to the Nazarov reaction, the cyclization of vinyl-cyclopropyl ketones is a stepwise process, often requiring harsh conditions. Herein, we describe two different approaches for further polarization of the three-membered ring of vinyl-cyclopropyl ketones to allow the formal homo-Nazarov reaction under mild catalytic conditions. In the first approach, the introduction of an ester group α to the carbonyl on the cyclopropane gave a more than tenfold increase in reaction rate, allowing us to extend the scope of the reaction to non-electron-rich aryl donor substituents in the β position to the carbonyl on the cyclopropane. In this case, a proof of principle for asymmetric induction could be achieved using chiral Lewis acid catalysts. In the second approach, heteroatoms, especially nitrogen, were introduced β to the carbonyl on the cyclopropane. In this case, the reaction was especially successful when the vinyl group was replaced by an indole heterocycle. With a free indole, the formal homo-Nazarov cyclization on the C3 position of indole was observed using a copper catalyst. In contrast, a new cyclization reaction on the N1 position was observed with BrAnsted acid catalysts. Both reactions were applied to the synthesis of natural alkaloids. Preliminary investigations on the rationalization of the observed regioselectivity are also reported.
- De Simone, Filippo,Saget, Tanguy,Benfatti, Fides,Almeida, Sofia,Waser, Jerome
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supporting information; experimental part
p. 14527 - 14538
(2012/02/04)
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- Copper-catalyzed cyanation of heterocycle carbon-hydrogen bonds
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A method for regioselective cyanation of heterocycles has been developed. A number of aromatic heterocycles as well as azulene can be cyanated in reasonable to good yields by using a copper cyanide catalyst and an iodine oxidant.
- Do, Hien-Quang,Daugulis, Olafs
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supporting information; experimental part
p. 2517 - 2519
(2010/08/07)
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- Copper-catalyzed arene C-H bond cross-coupling
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A highly regioselective, one-pot sequential iodination-copper-catalyzed cross-coupling of arene C-H bonds has been developed affording an efficient method for biaryl synthesis.
- Do, Hien-Quang,Daugulis, Olafs
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supporting information; experimental part
p. 6433 - 6435
(2010/03/04)
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- 2, (S)-α-(Methylpivaloylamino)bentyllithium-(-)-Sparteine, and 2: Crystal Structure Investigations of α-Lithiated Amines
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In order to determine whether α-metalated (lithiated) amines are carbenoids, as are α-lithiated halides and ethers, we have determined the crystal structures of the title compounds.In 2 (2) lithium bri
- Boche, Gernot,Marsch, Michael,Harbach, Juergen,Harms, Klaus,Ledig, Burkhard,et al.
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p. 1887 - 1894
(2007/10/02)
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