- Bismuth subnitrate-catalyzed markovnikov-type alkyne hydrations under batch and continuous flow conditions
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Bismuth subnitrate is reported herein as a simple and efficient catalyst for the atom-economical synthesis of methyl ketones via Markovnikov-type alkyne hydration. Besides an effective batch process under reasonably mild conditions, a chemically intensified continuous flow protocol was also developed in a packed-bed system. The applicability of the methodologies was demonstrated through hydration of a diverse set of terminal acetylenes. By simply switching the reaction medium from methanol to methanol-d4, valuable trideuteromethyl ketones were also prepared. Due to the ready availability and nontoxicity of the heterogeneous catalyst, which eliminated the need for any special additives and/or harmful reagents, the presented processes display significant advances in terms of practicality and sustainability.
- ?tv?s, Sándor B.,Fül?p, Ferenc,Szécsényi, Zsanett
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- Design of Development Candidate eFT226, a First in Class Inhibitor of Eukaryotic Initiation Factor 4A RNA Helicase
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Dysregulation of protein translation is a key driver for the pathogenesis of many cancers. Eukaryotic initiation factor 4A (eIF4A), an ATP-dependent DEAD-box RNA helicase, is a critical component of the eIF4F complex, which regulates cap-dependent protein synthesis. The flavagline class of natural products (i.e., rocaglamide A) has been shown to inhibit protein synthesis by stabilizing a translation-incompetent complex for select messenger RNAs (mRNAs) with eIF4A. Despite showing promising anticancer phenotypes, the development of flavagline derivatives as therapeutic agents has been hampered because of poor drug-like properties as well as synthetic complexity. A focused effort was undertaken utilizing a ligand-based design strategy to identify a chemotype with optimized physicochemical properties. Also, detailed mechanistic studies were undertaken to further elucidate mRNA sequence selectivity, key regulated target genes, and the associated antitumor phenotype. This work led to the design of eFT226 (Zotatifin), a compound with excellent physicochemical properties and significant antitumor activity that supports clinical development.
- Ernst, Justin T.,Thompson, Peggy A.,Nilewski, Christian,Sprengeler, Paul A.,Sperry, Samuel,Packard, Garrick,Michels, Theodore,Xiang, Alan,Tran, Chinh,Wegerski, Christopher J.,Eam, Boreth,Young, Nathan P.,Fish, Sarah,Chen, Joan,Howard, Haleigh,Staunton, Jocelyn,Molter, Jolene,Clarine, Jeff,Nevarez, Andres,Chiang, Gary G.,Appleman, Jim R.,Webster, Kevin R.,Reich, Siegfried H.
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supporting information
p. 5879 - 5955
(2020/07/03)
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- 1,4-Palladium Shift/C(sp3)-H Activation Strategy for the Remote Construction of Five-Membered Rings
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1,n-Metal shift is an elegant alternative approach enabling the functionalization of remote C-H bonds from simple precursors. In this work, we report a novel and simple Pd0-catalyzed domino reaction involving 1,4-palladium shift and C(sp3)-H activation and leading to (fused) five-membered rings. This method allowed access to a broad range of valuable arylidene γ-lactams and indanones and was applied to the formal synthesis of (-)-pyrrolam.
- Rocaboy, Ronan,Baudoin, Olivier
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supporting information
p. 1434 - 1437
(2019/02/19)
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- Air-stable μ2-hydroxyl bridged cationic binuclear complexes of zirconocene perfluorooctanesulfonates: their structures, characterization and application
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Three air-stable zirconocene perfluoro-octanesulfonates were successfully synthesized by treatment of C8F17SO3Ag with (RCp)2ZrCl2 [R = H, n-Bu, t-Bu]. According to X-ray analysis, they have μ2-hydroxyl bridged cationic binuclear structures: (i) [CpZr(OH2)3]2(μ2-OH)2(OSO2C8F17)4·2THF·4H2O (1a·2THF·4H2O), (ii) [n-BuCpZr(OH2)3]2(μ2-OH)2(OSO2C8F17)4·6H2O (2a·6H2O), and (iii) [t-BuCpZr(OH2)3]2(μ2-OH)2(OSO2C8F17)4·2C3H6O·8H2O (3a·2C3H6O·8H2O). The ligands of water and organic molecules in the complexes originated from the moist air and solvent during their recrystallization. These complexes were characterized with different techniques, and found to show water tolerance, air/thermal stability as well as strong Lewis acidity. Moreover, the complexes showed highly catalytic activity in various reactions of C–C bond formation. With good recyclability, they should find wide applications in organic chemistry.
- Zhang, Xiaohong,Xu, Xinhua,Li, Ningbo,Liang, Zhiwu,Tang, Zilong
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supporting information
p. 1926 - 1932
(2018/03/21)
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- Hydration of aromatic alkynes catalyzed by a self-assembled hexameric organic capsule
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The combination of a Br?nsted acid catalyst and a supramolecular organic capsule formed by the self-assembly of six resorcin[4]arene units efficiently promotes the mild hydration of aromatic alkynes to their corresponding ketones. The capsule provides a suitable nanoenvironment that favors protonation of the substrate and addition of water.
- La Sorella, Giorgio,Sperni, Laura,Ballester, Pablo,Strukul, Giorgio,Scarso, Alessandro
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p. 6031 - 6036
(2016/08/05)
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- Metal Sulfonate Polymers as Catalysts for the Heterogeneous Acylation of Aromatic Derivatives
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A series of metal sulfonate salts attached to a poly(ether ether ketone) (PEEK) polymer were prepared by ultrasonic activation and then examined as heterogeneous catalysts in the Friedel–Crafts acylation of aromatic derivatives.
- Morizur, Vincent,Hector, Daphné,Olivero, Sandra,Desmurs, Jean Roger,Du?ach, Elisabet
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supporting information
p. 3126 - 3129
(2016/07/12)
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- Pyrazolyl-Based Carboxamides II
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The invention relates to pyrazolyl-based carboxamide compounds useful as ICRAC inhibitors, to pharmaceutical compositions containing these compounds and to these compounds for the use in the treatment and/or prophylaxis of diseases and/or disorders, in particular inflammatory diseases and/or inflammatory disorders.
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Paragraph 0434-0436; 0457-0458
(2014/07/22)
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- PYRAZOLYL-BASED CARBOXAMIDES II AS CRAC CHANNEL INHIBITORS
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The invention relates to pyrazolyl-based carboxamide compounds of formula (I) useful as ICRAC inhibitors, to pharmaceutical compositions containing these compounds and to these compounds for the use in the treatment and/or prophylaxis of diseases and/or disorders, in particular inflammatory diseases and/or inflammatory disorders.
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Page/Page column 56; 59
(2014/07/23)
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- Strong Lewis acid air-stable cationic titanocene perfluoroalkyl(aryl) sulfonate complexes as highly efficient and recyclable catalysts for C-C bond forming reactions
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A series of strong Lewis acid air-stable titanocene perfluoroalkyl(aryl) sulfonate complexes Cp2Ti(OH2)2(OSO 2X)2·THF (X = C8F17, 1·THF; X = C4F9, 2·H2O· THF; X = C6F5, 3) were successfully synthesized by the treatment of Cp2TiCl2 with C8F 17SO3Ag, C4F9SO3Ag and C6F5SO3Ag, respectively. In contrast to well-known titanocene bis(triflate), these complexes showed no change in open air over three months. TG-DSC analysis showed that 1·THF, 2·H 2O·THF and 3 were thermally stable at 230 °C, 220°C and 280°C, respectively. Conductivity measurements showed that these complexes underwent ionic dissociation in CH3CN solution. X-ray analysis results confirmed that 2·H2O·THF and 3 were cationic. ESR spectra showed that the Lewis acidity of 1·THF (1.06 eV) was higher than that of Sc3+ (1.00 eV) and Y3+ (0.85 eV). UV/Vis spectra showed a significant red shift due to the strong complex formation between 10-methylacridone and 2·H2O·THF. Fluorescence spectra showed that the Lewis acidity of 2 (λem = 477 nm) was higher than that of Sc3+ (λem = 474 nm). These complexes showed high catalytic ability in various carbon-carbon bond forming reactions. Moreover, they show good reusability. Compared with 1·THF, 2·H2O·THF and 3 exhibit higher solubility and better catalytic activity, and will find broad applications in organic synthesis. This journal is the Partner Organisations 2014.
- Li, Ningbo,Wang, Jinying,Zhang, Xiaohong,Qiu, Renhua,Wang, Xie,Chen, Jinyang,Yin, Shuang-Feng,Xu, Xinhua
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supporting information
p. 11696 - 11708
(2014/07/22)
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- Synthesis and structure of an air-stable μ2-hydroxy-bridged binuclear complex of bis(methylcyclopentadienyl)dizirconium(IV) perfluorooctanesulfonate and its application in Lewis acid-catalyzed reactions
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Air-stable binuclear complex of bis(methylcyclopentadienyl)zirconium perfluorooctanesulfonate (1a) was successfully synthesized by the reaction of (CH3Cp)2ZrCl2 with C8F 17SO3Ag. The compound 1a was characterized by different techniques and found to have the nature of air-stability, water tolerance, thermally-stability and strong Lewis-acidity. In addition, its solubility was higher than that of our previously reported uninuclear zirconocene bis(perfluorooctanesulfonate). It showed high catalytic efficiency in the Friedel-Crafts acylation of alkyl aryl ethers and the Mannich reaction and could be reused.
- Zhang, Xiaohong,Lou, Cong,Li, Ningbo,Xu, Xinhua,Qiu, Renhua,Yin, Shuangfeng
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supporting information
p. 241 - 245
(2013/11/06)
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- AgOTf catalyzed hydration of terminal alkynes
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The silver catalysis towards the hydration of terminal alkynes is explored using Silver(I) triflate (AgOTf). The reaction leads to the formation of only Markovnikov addition product with excellent yield. Copyright
- Das, Rima,Chakraborty, Debashis
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p. 722 - 726
(2013/02/22)
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- Synthesis and structure of an extremely air-stable binuclear hafnocene perfluorooctanesulfonate complex and its use in lewis acid-catalyzed reactions
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An extremely air-stable μ2-hydroxy-bridged binuclear hafonocene perfluorooctanesulfoante complex was successfully synthesized. This complex showed high catalytic efficiency in the esterification of alcohols, phenol, thiol, and amines, in the Friedel-Crafts acylation of alylaryl ethers, in the Mukaiyama aldol reaction, and in the allylation of aldehydes and could be reused.
- Qiu, Renhua,Zhang, Guoping,Zhu, Yuyang,Xu, Xinhua,Shao, Lingling,Li, Yinhui,An, Delie,Yin, Shuangfeng
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supporting information; scheme or table
p. 6488 - 6494
(2010/02/28)
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- Unexpectedly high activity of Zn(OTf)2·6H2O in catalytic Friedel-Crafts acylation reaction
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Zn(OTf)2·6H2O was used to promote Friedel-Crafts acylation of aromatics. The work describes the high activity and efficiency of Zn(OTf)2·6H2O in acylation of aromatics, and the catalyst has surpassed most metal triflates in dispensing when dried at high temperature under vacuum before use. Copyright Taylor & Francis Group, LLC.
- He, Fei,Wu, Huayue,Chen, Jiuxi,Su, Weike
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p. 255 - 264
(2008/03/17)
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- 1-THIO-D-GLUCITOL DERIVATIVES
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The present invention provides a 1-thio-D-glucitol compound of the following formula, which shows the action of inhibiting the activity of SGLT2, a pharmaceutically acceptable salt of the compound, or a hydrate of the compound or the salt; and a pharmaceu
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Page/Page column 40-41
(2010/11/28)
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- Catalytic Friedel-Crafts acylation of aromatic ethers using Sml3
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10% mol Sml3 catalysed the Friedel-Crafts acylation of aromatic ethers by acyl chlorides in acetonitrile with the yields of 48-82%. Reactions of various substituted aromatic ethers with acyl chloride were studied. The structures of compounds were established by IR and 1H NMR. The main product obtained with anisole is the para-substituted compound with only a trace (3, a pattern repeated with the other aromatic ethers used.
- Chen, Xiaohang,Yu, Mingxin,Wang, Meijun
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- Acetylation of aromatic ethers using acetic anhydride over solid acid catalysts in a solvent-free system. Scope of the reaction for substituted ethers
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The acetylation of aryl ethers using acetic anhydride in the presence of zeolites under modest conditions in a solvent-free system gave the corresponding para-acetylated products in high yields. The zeolite can be recovered, regenerated and reused to give almost the same yields as that given when fresh zeolite is used.
- Smith, Keith,El-Hiti, Gamal A.,Jayne, Anthony J.,Butters, Michael
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p. 1560 - 1564
(2007/10/03)
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- LiClO4-acyl anhydrides complexes as powerful acylating reagents of aromatic compounds in solvent free conditions
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The Friedel-Crafts acylation of various activated benzenes is smoothly carried out with acyl anhydrides in the presence of 2 equiv. of LiClO4, as reaction promoter, under solventless conditions.
- Bartoli, Giuseppe,Bosco, Marcella,Marcantoni, Enrico,Massaccesi, Massimo,Rinaldi, Samuele,Sambri, Letizia
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p. 6331 - 6333
(2007/10/03)
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- Alkyl tetralin aldehyde compounds
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The present invention relates, inter alia, to novel alkyl tetralin aldehyde compounds having fragrant musk-like aroma.
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- Tetralin formate ester aroma chemicals
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The present invention relates to novel formate ester tetralin compounds having fragrant musk-like aroma.
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- Structural Effects on Selective Aliphatic Hydrogen Exchange in Alkyl-Substituted Aromatic Compounds in Deuteriated Trifluoroacetic Acid
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A qualitative study has been carried out concerning structural effects on selective aliphatic hydrogen exchange for a variety of alkylated aromatic compounds in deuteriated trifluoroacetic acid.It has been observed that the β-hydrogen exchange in isopropy
- Nilsson, Ake,Nilsheden, Claes
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- ORTHO METALATION DIRECTED BY α-AMINO ALKOXIDES. AN IMPROVED SYNTHESIS OF ORTHO-SUBSTITUTED ARYL KETONES
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Ortho-substituted aryl ketones are prepared from N--N-methylbenzamides via ortho lithiation of intermediate α-amino alkoxides, formed in situ by addition of RLi.An ortho lithiation of N--N-methylbenzamide is also described.
- Comins, Daniel L.,Brown, Jack D.
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p. 5465 - 5468
(2007/10/02)
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- 13C NMR Shifts and Conformations of Substituted Indans
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13C NMR spectra of indan derivatives bearing substituents in the 1,2,5 and 6 positions are reported and assigned by LIS measurements and other techniques.Epimeric indanes bearing vicinal oxygen and phenyl or benzyl susbtituents show ring carbon shielding in the cis relative to the trans isomers, which is compared with corresponding cyclopentane shifts, and indicates the predominance of envelope confomations with pseudoaxial oxygen substituents for the cis isomers.Acetylation shifts show consistently larger shielding at pseudoaxial oxygen substituents for the cis isomers.Acetylation shifts show consistently larger shielding at C-β for the trans compounds.Introduction of oxygen at C-5 leads to asymmetric shielding effects at the ortho carbon atoms as soon as there is a substituent in the para position which can participate in mesomeric forms.
- Agrawal, Pawan Kumar,Schneider, Hans-Joerg,Malik, Mangel S.,Rastogi, Shri Nivas
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p. 146 - 150
(2007/10/02)
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- Vinyl Cation Intermediates in Solvolytic and Electrophilic Reactions. 1. Solvolysis of α-Arylvinyl Derivatives
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The solvolysis of 16 α-arylvinyl tosylates, bromides, and chlorides has been investigated in various alcohol-water mixtures and in acetic acid at several temperatures.All substrates were substituted with either 2-methyl or 2,6-dimethyl groups to accelerate the rates of reaction.The major or exclusive product isolated in most cases was the acetophenone arising from hydrolysis of the expected enol ethers or acetates during workup.The kinetics were simple first order in the vast majority of cases, with excess base added to prevent side reactions.Leaving group effects, Winstein-Grunwald m values, Schleyer Q values, and effects of solvent nucleophilicity all point to a limiting SN1 ionization generating a vinyl cation intermediate, in which there is little rear-side nucleophilic assistance by solvent.Substituent effects led to ρ values in the range -3.9 to -5.3 vs. ?+.Activation parameters are typical for an SN1 process, and ΔS% is insensitive to the presence of zero, one, or two o-methyl groups, as are the effects of solvent polarity on the rates.The results should therefore be directly comparable with other solvolytic or electrophilic reactions generating formally similar vinyl cation intermediates.
- Yates, Keith,Mandrapilias, George
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p. 3892 - 3902
(2007/10/02)
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