- β-sheet-like hydrogen bonds interlock the helical turns of a photoswitchable foldamer to enhance the binding and release of chloride
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Inspired by halorhodopsins use of photoisomerization to regulate chloride, aryltriazole-based foldamers have been created to "catch and release" chloride ions upon light irradiation of end-appended azobenzenes. The proposed mode of stabilization exploits a β-sheet-like hydrogen-bonding array to cooperatively interlock the ends of a foldamer together with its helical core. We find that the hydrogen-bonding array has a greater influence on stabilizing the helix than the π-stacked seam under the conditions examined (50:50 MeCN/THF). Thus, we show how it is possible to enhance the difference between Cl- binding and release using light-dependent control over the foldamers degree of helix stabilization. Making and breaking three π-π contacts with light caused an 8-fold change in chloride affinity (40 300 M-1 ? 5000 M-1), five π-π contacts produced a 17-fold change (126 000 M-1 ? 7400 M-1), and strategically located hydrogen-bonding units enabled a greater 84-fold differential (970 000 M-1 ? 11 600 M-1). The improved performances were attributed to stepwise increases in the preorganization of the binding pocket that catches chloride while leaving the cis states with just one π-π contact relatively unchanged.
- Lee, Semin,Hua, Yuran,Flood, Amar H.
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Read Online
- Facile synthesis of para-[18F]fluorohippurate via iodonium ylide-mediated radiofluorination for PET renography
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para-[18F]fluorohippurate ([18F]PFH) is a renal tubular agent suitable for conducting positron emission tomography (PET) renography. [18F]PFH is currently synthesized by a four-step two-pot procedure utilizing a classical
- Nkepang, Gregory N.,Hedrick, Andria F.,Awasthi, Vibhudutta,Gali, Hariprasad
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- Benzoylsalicylic acid derivatives as defense activators in tobacco and Arabidopsis
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Systemic acquired resistance (SAR) is a long lasting inducible whole plant immunity often induced by either pathogens or chemical elicitors. Salicylic acid (SA) is a known SAR signal against a broad spectrum of pathogens in plants. In a recent study, we have reported that benzoylsalicylic acid (BzSA) is a SAR inducer in tobacco and Arabidopsis plants. Here, we have synthesized BzSA derivatives using SA and benzoyl chlorides of various moieties as substrates. The chemical structures of BzSA derivatives were elucidated using Infrared spectroscopy (IR), Nuclear magnetic spectroscopy (NMR) and High-resolution mass spectrometer (HRMS) analysis. The bioefficacy of BzSA derivatives in inducing defense response against tobacco mosaic virus (TMV) was investigated in tobacco and SA abolished transgenic NahG Arabidopsis plants. Interestingly, pre-treatment of local leaves of tobacco with BzSA derivatives enhanced the expression of SAR genes such as NPR1 [Non-expressor of pathogenesis-related (PR) genes 1], PR and other defense marker genes (HSR203, SIPK, WIPK) in systemic leaves. Pre-treatment of BzSA derivatives reduced the spread of TMV infection to uninfected areas by restricting lesion number and diameter both in local and systemic leaves of tobacco in a dose-dependent manner. Furthermore, pre-treatment of BzSA derivatives in local leaves of SA deficient Arabidopsis NahG plants induced SAR through AtPR1 and AtPR5 gene expression and reduced leaf necrosis and curling symptoms in systemic leaves as compared to BzSA. These results suggest that BzSA derivatives are potent SAR inducers against TMV in tobacco and Arabidopsis.
- Kamatham, Samuel,Pallu, Reddanna,Pasupulati, Anil Kumar,Singh, Surya Satyanarayana,Gudipalli, Padmaja
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Read Online
- Unifying the Aminohexopyranose- and Peptidyl-Nucleoside Antibiotics: Implications for Antibiotic Design
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In search of new anti-tuberculars compatible with anti-retroviral therapy we re-identified amicetin as a lead compound. Amicetin's binding to the 70S ribosomal subunit of Thermus thermophilus (Tth) has been unambiguously determined by crystallography and
- Barrows, Louis R.,Eiler, Daniel,Kanna Reddy, Hariprasada Reddy,Koch, Michael,Looper, Ryan E.,Sebahar, Paul R.,Serrano, Catherine M.,Testa, Charles A.,Tresco, Ben I. C.,VanderLinden, Ryan T.
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- Supramolecular bidentate phosphine ligand scaffolds from deconstructed Hamilton receptors
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There is constant demand for new ligand archictectures on which inorganic and organometallic structures can be leveraged. An important, but often synthetically challenging, class of ligands is bidentate phosphines. Here we report self-assembling, supramolecular bidentate ligand scaffolds based on deconstructed Hamilton receptors with binding affinities up to 800 ± 100 M-1
- Seidenkranz, Daniel T.,McGrath, Jacqueline M.,Zakharov, Lev N.,Pluth, Michael D.
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- Chemical Proteomics and Phenotypic Profiling Identifies the Aryl Hydrocarbon Receptor as a Molecular Target of the Utrophin Modulator Ezutromid
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Duchenne muscular dystrophy (DMD) is a fatal muscle-wasting disease arising from mutations in the dystrophin gene. Upregulation of utrophin to compensate for the missing dystrophin offers a potential therapy independent of patient genotype. The first-in-class utrophin modulator ezutromid/SMT C1100 was developed from a phenotypic screen through to a Phase 2 clinical trial. Promising efficacy and evidence of target engagement was observed in DMD patients after 24 weeks of treatment, however trial endpoints were not met after 48 weeks. The objective of this study was to understand the mechanism of action of ezutromid which could explain the lack of sustained efficacy and help development of new generations of utrophin modulators. Using chemical proteomics and phenotypic profiling we show that the aryl hydrocarbon receptor (AhR) is a target of ezutromid. Several lines of evidence demonstrate that ezutromid binds AhR with an apparent KD of 50 nm and behaves as an AhR antagonist. Furthermore, other reported AhR antagonists also upregulate utrophin, showing that this pathway, which is currently being explored in other clinical applications including oncology and rheumatoid arthritis, could also be exploited in future DMD therapies.
- Wilkinson, Isabel V. L.,Perkins, Kelly J.,Dugdale, Hannah,Moir, Lee,Vuorinen, Aini,Chatzopoulou, Maria,Squire, Sarah E.,Monecke, Sebastian,Lomow, Alexander,Geese, Marcus,Charles, Philip D.,Burch, Peter,Tinsley, Jonathan M.,Wynne, Graham M.,Davies, Stephen G.,Wilson, Francis X.,Rastinejad, Fraydoon,Mohammed, Shabaz,Davies, Kay E.,Russell, Angela J.
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- Immobilization of (l)-valine and (l)-valinol on SBA-15 nanoporous silica and their application as chiral heterogeneous ligands in the Cu-catalyzed asymmetric allylic oxidation of alkenes
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SBA-15 nanoporous silica was synthesized by hydrothermal method using P123 surfactant and tetraethoxyortosilicate in acidic condition and then functionalized by 3-chloropropyltrimethoxysilane. Next, by immobilization of chiral amino acid (S)-2-amino-3-methyl butanoic acid (l-valine) and chiral amino alcohol (S)-2-amino-3-methylbutane-1-ol (l-valinol), preparedviathe reduction ofl-valine by NaBH4/I2in THF, on functionalized-SBA-15, chiral heterogeneous ligands AL*-i-Pr-SBA-15 and AA*-i-Pr-SBA-15 were prepared and characterized by FT-IR, XRD, TGA, EDX, SEM, BET-BJH techniques. The asymmetric allylic oxidation of alkenes was done using copper-complexes of these ligands and the as-synthesized peresters. The reactions were optimized by varying various parameters such as temperature, solvent, amount of chiral heterogeneous ligand, as well as the type and amount of copper salt. Under optimized conditions, 6 mg of AL*-i-Pr-SBA-15 and 3.2 mol% of Cu(CH3CN)4PF6in acetonitrile at 50 °C, the chiral allylic ester was obtained with 80% yield and 39% enantiomeric excess in 24 h. The recyclability of the chiral heterogeneous catalysts was also evaluated without significant reduction in the reaction results up to three runs.
- Ashouri, Akram,Mahramasrar, Mahsa,Majidian, Shiva,Rashid, Hersh I,Samadi, Saadi
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supporting information
p. 17630 - 17641
(2021/10/04)
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- Synthesis of new alkenyl iodobenzoate derivatives via Kharasch-Sosnovsky reaction using tert-butyl iodo benzoperoxoate and copper (I) iodide
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Abstract: The synthesis of new alkenyl iodobenzoate derivatives as allylic esters was investigated via the reaction of tert-butyl iodobenzoperoxoate with alkenes in the presence of copper salts. The best result was obtained using tert-butyl-iodobenzoperoxoate in the presence of copper (I) iodide (5?mol%) in refluxing acetonitrile with good yield (92%) in 32?h. The structure of peresters and alkenyl iodobenzoate derivatives were characterized on the basis of their FT-IR, 1HNMR, 13CNMR, and Mass spectra. Graphic abstract: The preparation of new iodo-allylic esters from alkenes in the presence of copper salts in good to excellent yields is reported in this article.[Figure not available: see fulltext.]
- Samadi, Saadi,Ashouri, Akram,Majidian, Shiva,I Rashid, Hersh
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- Using in vitro lipolysis and SPECT/CT in vivo imaging to understand oral absorption of fenofibrate from lipid-based drug delivery systems
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Using lipid-based drug delivery systems (LbDDS) is an efficient strategy to enhance the low oral bioavailability of poorly water-soluble drugs. Here the oral absorption of fenofibrate (FF) from LbDDS in rats was investigated in pharmacokinetic, in vitro l
- Tran, Thuy,B?nl?kke, Peter,Rodríguez-Rodríguez, Cristina,Nosrati, Zeynab,Esquinas, Pedro Luis,Borkar, Nrupa,Plum, Jakob,Strindberg, Sophie,Karagiozov, Stoyan,Rades, Thomas,Müllertz, Anette,Saatchi, Katayoun,H?feli, Urs O.
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p. 375 - 384
(2019/12/25)
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- Electrochemical intramolecular C-H/N-H functionalization for the synthesis of isoxazolidine-fused isoquinolin-1(2: H)-ones
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A general and practical protocol for the construction of isoxazolidine-fused isoquinolin-1(2H)-ones has been described by electrochemical-oxidation-induced intramolecular annulation via amidyl radicals. In an undivided cell, isoquinolinones could be easily generated from various available amides bearing CONHOR groups under metal-free, additive-free and external oxidant-free conditions. Moreover, this transformation proceeded smoothly by using cheap 95% ethanol as the green solvent and could be extended to the gram scale.
- Zhang, Lin-Bao,Geng, Rui-Sen,Wang, Zi-Chen,Ren, Guang-Yi,Wen, Li-Rong,Li, Ming
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supporting information
p. 16 - 21
(2020/01/13)
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- Copper-catalyzed and additive free decarboxylative trifluoromethylation of aromatic and heteroaromatic iodides
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A copper-catalyzed decarboxylative trifluoromethylation of (hetero)aromatic iodides has been developed. Importantly, this new copper-catalyzed reaction operates in the absence of any ligands and metal additives. The protocol shows good functional group tolerance and is compatible with heteroaromatic systems. The reaction proved scalable to a 15 mmol scale with increased yield. Finally, late-stage installation of the trifluoromethyl functionality afforded the N-trifluoroacetamide variant of the antidepressant agent, Prozac, demonstrating the applicability of the developed method.
- Johansen, Martin B.,Lindhardt, Anders T.
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supporting information
p. 1417 - 1425
(2020/03/03)
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- Chemoselective Cross-Coupling of gem-Borazirconocene Alkanes with Aryl Halides
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The direct and chemoselective conversion of the carbon-metal bond of gem-dimetallic reagents enables rapid and sequential formation of multiple carbon-carbon and carbon-heteroatom bonds, thus representing a powerful method for efficiently increasing structural complexity. Herein, we report a visible-light-induced, nickel-catalyzed, chemoselective cross-coupling reaction between gem-borazirconocene alkanes and diverse aryl halides, affording a wide range of alkyl Bpin derivatives in high yields with excellent regioselectivity. This practical method features attractively simple reaction conditions and a broad substrate scope. Additionally, we systematically investigated a Bpin-directed chain walking process underlying the regioselectivity of alkylzirconocenes, thus uncovering the mechanism of the remote functionalization of internal olefins achieved with our method. Finally, DFT calculations indicate that the high regioselectivity of this reaction originates from the directing effect of the Bpin group.
- Bai, Songlin,Gao, Yadong,Jiang, Chao,Qi, Xiangbing,Yang, Chao
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supporting information
p. 11506 - 11513
(2020/07/14)
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- ANTIMICROBIAL COMPOUNDS
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Disclosed are compounds of formula I: or pharmaceutically acceptable salts thereof. Compounds of formula I are anti-microbials that inhibit, for instance, Mycobacterium tuberculosis (Mtb) H37Ra. Compounds of formula I also have anti-tubercular activity, e
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Page/Page column 00225; 00226
(2019/02/02)
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- Aerobic C(sp2)-H Hydroxylations of 2-Aryloxazolines: Fast Access to Excited-State Intramolecular Proton Transfer (ESIPT)-Based Luminophores
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The direct hydroxylation of 2-aryloxazolines via a deprotonative magnesiation using TMPMgCl·LiCl and subsequent oxidation with molecular oxygen or air as a green oxidant is reported. This method proceeds under mild conditions at room temperature with high regioselectivity and chemoselectivity. The obtained phenols exhibit tunable luminescence properties, induced by excited-state intramolecular proton transfer. This method opens a new opportunity for the sustainable synthesis of luminescent organic molecules.
- G?bel, Dominik,Clamor, Nils,Lork, Enno,Nachtsheim, Boris J.
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supporting information
p. 5373 - 5377
(2019/06/07)
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- Ligand-Promoted RhIII-Catalyzed Thiolation of Benzamides with a Broad Disulfide Scope
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A ligand-promoted RhIII-catalyzed C(sp2)?H activation/thiolation of benzamides has been developed. Using bidentate mono-N-protected amino acid ligands led to the first example of RhIII-catalyzed aryl thiolation reactions directed by weakly coordinating directing amide groups. The reaction tolerates a broad range of amides and disulfide reagents.
- Kang, Yan-Shang,Zhang, Ping,Li, Min-Yan,Chen, You-Ke,Xu, Hua-Jin,Zhao, Jing,Sun, Wei-Yin,Yu, Jin-Quan,Lu, Yi
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supporting information
p. 9099 - 9103
(2019/06/13)
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- Rhenium-Catalyzed Phthalide Synthesis from Benzamides and Aldehydes via C-H Bond Activation
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The [4 + 1] annulation of benzamides and aldehydes for phthalide synthesis was achieved via rhenium-catalyzed C-H activation, which demonstrates an unprecedented reaction pattern distinct from those of other transition-metal catalyses. The reaction also features readily available starting materials, a wide scope for both electro-rich and electro-deficient substrates, and the elimination of homoannulation byproducts.
- Jia, Bing,Yang, Yunhui,Jin, Xiqing,Mao, Guoliang,Wang, Congyang
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supporting information
p. 6259 - 6263
(2019/09/06)
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- Facile synthesis of 3(2H)-furanones
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Abstract: A practical method for the synthesis of 3(2H)-furanones including the bullatenone was described. Intramolecular cyclization of 4-hydroxyalkynones in the presence of KOH affords the biologically potent furanones in moderate-to-good yield at room temperature. Synthesis of 4-hydroxyalkynones from the reaction of acid chloride and terminal alkyne in the presence of copper iodide at room temperature was also reported.
- Panda, Niranjan,Nayak, Dinesh K.
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p. 1093 - 1100
(2018/02/22)
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- Pharmaceutical-Oriented Methoxylation of Aryl C(sp 2)-H Bonds using Copper Catalysts
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A pharmaceutical-oriented, copper(II)-catalyzed methoxylation of aryl C(sp 2)-H bonds has been developed. This simple and environmentally benign reaction system occurs efficiently using oxygen as oxidant with broad substrate scope and high functional group tolerance.
- Zhang, Guofu,Zhu, Jianfei,Tong, Chaolai,Ding, Chengrong
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supporting information
p. 1451 - 1454
(2018/05/14)
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- COMPOUNS, COMPOSITIONS AND METHODS OF USE
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Herein, compounds, compositions and methods for modulating inclusion formation and stress granules in cells related to the onset of neurodegenerative diseases, musculoskeletal diseases, cancer, ophthalmological diseases, and viral infections are described.
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Page/Page column 100; 101
(2018/07/29)
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- Synthesis of phthalic acid derivatives: Via Pd-catalyzed alkoxycarbonylation of aromatic C-H bonds with alkyl chloroformates
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A Pd(ii)-catalyzed alkoxycarbonylation of aromatic C-H bonds with alkyl chloroformates has been developed. A broad range of benzamides and alkyl chloroformates are compatible with this protocol. The reaction is operationally simple and scalable. The direct group could be readily removed to access substituted phthalic acid esters (PAEs), 1,2-dibenzyl alcohols and phthalamides. Besides alkoxycarbonylation of benzamide β-C-H bonds, γ-alkoxycarbonylation of 2-phenylacetamide is also feasible.
- Liao, Gang,Chen, Hao-Ming,Shi, Bing-Feng
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supporting information
p. 10859 - 10862
(2018/10/02)
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- Discovery of a Potent Thiazolidine Free Fatty Acid Receptor 2 Agonist with Favorable Pharmacokinetic Properties
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Free fatty acid receptor 2 (FFA2/GPR43) is a receptor for short-chain fatty acids reported to be involved in regulation of metabolism, appetite, fat accumulation, and inflammatory responses and is a potential target for treatment of various inflammatory and metabolic diseases. By bioisosteric replacement of the central pyrrolidine core of a previously disclosed FFA2 agonist with a synthetically more tractable thiazolidine, we were able to rapidly synthesize and screen analogues modified at both the 2- and 3-positions on the thiazolidine core. Herein, we report SAR exploration of thiazolidine FFA2 agonists and the identification of 31 (TUG-1375), a compound with significantly increased potency (7-fold in a cAMP assay) and reduced lipophilicity (50-fold reduced clogP) relative to the pyrrolidine lead structure. The compound has high solubility, high chemical, microsomal, and hepatocyte stability, and favorable pharmacokinetic properties and was confirmed to induce human neutrophil mobilization and to inhibit lipolysis in murine adipocytes.
- Hansen, Anders H?jgaard,Sergeev, Eugenia,Bolognini, Daniele,Sprenger, Richard R.,Ekberg, Jeppe Hvidtfeldt,Ejsing, Christer S.,McKenzie, Christine J.,Rexen Ulven, Elisabeth,Milligan, Graeme,Ulven, Trond
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supporting information
p. 9534 - 9550
(2018/10/24)
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- Electronic Decoupling in C3-Symmetrical Light-Responsive Tris(Azobenzene) Scaffolds: Self-Assembly and Multiphotochromism
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We report the synthesis of a novel C3-symmetrical multiphotochromic molecule bearing three azobenzene units at positions 1, 3, 5 of the central phenyl ring. The unique geometrical design of such a rigid scaffold enables the electronic decouplin
- Galanti, Agostino,Diez-Cabanes, Valentin,Santoro, Jasmin,Valá?ek, Michal,Minoia, Andrea,Mayor, Marcel,Cornil, Jér?me,Samorì, Paolo
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supporting information
p. 16062 - 16070
(2018/11/23)
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- 2-Iodo-N-isopropyl-5-methoxybenzamide as a highly reactive and environmentally benign catalyst for alcohol oxidation
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Several N-isopropyliodobenzamides were evaluated as catalysts for the oxidation of benzhydrol to benzophenone in the presence of Oxone (2KHSO5·KHSO4·K2SO4) as a co-oxidant at room temperature. A study on the substituent effect of the benzene ring of N-isopropyl-2-iodobenzamide on the oxidation revealed that its reactivity increased in the following order of substitution: 5-NO2 2Me, 3-OMe 5-OAc 5-Cl H, 4-OMe 5-Me 5-OMe. The oxidation of various benzylic and aliphatic alcohols using a catalytic amount of the most reactive 5-methoxy derivative successfully resulted in moderate to excellent yields of the corresponding carbonyl compounds. The high reactivity of the 5-methoxy derivative at room temperature is a result of the rapid generation of the pentavalent species from the trivalent species during the reaction. 5-Methoxy-2-iodobenzamide would be an efficient and environmentally benign catalyst for the oxidation of alcohols, especially benzylic alcohols.
- Yakura, Takayuki,Fujiwara, Tomoya,Yamada, Akihiro,Nambu, Hisanori
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supporting information
p. 971 - 978
(2019/11/11)
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- Functional Group Transposition: A Palladium-Catalyzed Metathesis of Ar-X σ-Bonds and Acid Chloride Synthesis
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We describe the development of a new method to use palladium catalysis to form functionalized aromatics: via the metathesis of covalent σ-bonds between Ar-X fragments. This transformation demonstrates the dynamic nature of palladium-based oxidative addition/reductive elimination and offers a straightforward approach to incorporate reactive functional groups into aryl halides through exchange reactions. The reaction has been exploited to assemble acid chlorides without the use of high energy halogenating or toxic reagents and, instead, via the metathesis of aryl iodides with other acid chlorides.
- De La Higuera Macias, Maximiliano,Arndtsen, Bruce A.
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supporting information
p. 10140 - 10144
(2018/08/23)
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- Metathesis-active ligands enable a catalytic functional group metathesis between aroyl chlorides and aryl iodides
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Current methods for functional group interconversion have, for the most part, relied on relatively strong driving forces which often require highly reactive reagents to generate irreversibly a desired product in high yield and selectivity. These approaches generally prevent the use of the same catalytic strategy to perform the reverse reaction. Here we describe a catalytic functional group metathesis approach to interconvert, under CO-free conditions, two synthetically important classes of electrophiles that are often employed in the preparation of pharmaceuticals and agrochemicals—aroyl chlorides (ArCOCl) and aryl iodides (ArI). Our reaction design relies on the implementation of a key reversible ligand C–P bond cleavage event, which enables a non-innocent, metathesis-active phosphine ligand to mediate a rapid aryl group transfer between the two different electrophiles. Beyond enabling a practical and safer approach to the interconversion of ArCOCl and ArI, this type of ligand non-innocence provides a blueprint for the development of a broad range of functional group metathesis reactions employing synthetically relevant aryl electrophiles.
- Lee, Yong Ho,Morandi, Bill
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p. 1016 - 1022
(2018/09/06)
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- IODONIUM SALT COMPOUND, PHOTOACID GENERATOR AND COMPOSITION CONTAINING THE SAME, AND METHOD FOR MANUFACTURING DEVICE
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PROBLEM TO BE SOLVED: To provide an iodonium salt compound which can be used as a chemical amplification type photoacid generator for resist and a photocationic polymerization initiator, has high sensitivity to an i-line at a wavelength of 365 nm, and has high solubility to an organic solvent and a resin. SOLUTION: A new iodonium salt compound is represented by the following iodonium salts 2, 5 and 10. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0086; 0088; 0142; 0143; 0144
(2019/01/06)
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- TETRAHYDROISOQUINOLINE ESTROGEN RECEPTOR MODULATORS AND USES THEREOF
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Described herein are tetrahydroisoquinoline compounds with estrogen receptor modulation activity or function having the Formula I structure: I and stereoisomers, tautomers, or pharmaceutically acceptable salts thereof, and with the substituents and structural features described herein. Also described are pharmaceutical compositions and medicaments that include the Formula I compounds, as well as methods of using such estrogen receptor modulators, alone and in combination with other therapeutic agents, for treating diseases or conditions that are mediated or dependent upon estrogen receptors.
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Page/Page column 75; 76; 102
(2017/11/06)
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- POST-FUNCTIONALIZATION OF SUPRAMOLECULAR MATERIALS
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The present invention relates to a supramolecular material which can be functionalized, in particular surface-functionalized, by an orthogonal reaction with a compound comprising a functionalizing group. The supramolecular material according to the present invention comprises acompound (a) and compound (b), wherein -compound (a) comprises at least two supramolecular subunits S(a) linked by a linker L(a) comprising a polymer P(a), and -compound (b) comprises a supramolecular subunit S(b) and a first orthogonal reaction partner O1 capable of forming a covalent bond to a second orthogonal reaction partner O2. Upon functionalization, the supramolecular material according to the invention, O1 of compound (b) is covalently linked to an O2 in a compound (c), wherein compound (c) comprises an O2 and a functionalizing group F.The invention also relates to a method for the preparation of the supramolecular material and use of the supramolecular material as a biomaterial.
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Page/Page column 39; 40
(2017/12/01)
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- Crystal engineering of hand-twisted helical crystals
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A strategy is outlined for the design of hand-twisted helical crystals. The starting point in the exercise is the one-dimensional (1D) plastic crystal, 1,4-dibromobenzene, which is then changed to a 1D elastic crystal, exemplified by 4-bromophenyl 4'-chlorobenzoate, by introduction of a molecular synthon -O-CO-in lieu of the supramolecular synthon Br···Br in the precursor. The 1D elastic crystals are next modified to two-dimensional (2D) elastic crystals, of the type 4-bromophenyl 4'-nitrobenzoate where the halogen bonding and C-H· · ·O hydrogen bonding are well-matched. Finally, varying the interaction strengths in these 2D elastic crystals gives plastic crystals with two pairs of bendable faces but without slip planes. Typical examples are 4-chlorophenyl and 4-bromophenyl 4'-nitrobenzoate. This type of 2D plasticity represents a new type of bendable crystals in which plastic behavior is seen with a fair degree of isotropic character in the crystal packing. The presence of two sets of bendable faces, generally orthogonal to each other, allows for the possibility of hand-twisting of the crystals to give grossly helical morphologies. Accordingly, we propose the name hand-twisted helical crystals for these substances.
- Saha, Subhankar,Desiraju, Gautam R.
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supporting information
p. 1975 - 1983
(2017/02/15)
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- Irreversible Cysteine-Selective Protein Labeling Employing Modular Electrophilic Tetrafluoroethylation Reagents
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Fluoroalkylation reagents based on hypervalent iodine are widely used to transfer fluoroalkyl moieties to various nucleophiles. However, the transferred groups have so far been limited to simple structural motifs. We herein report a reagent featuring a secondary amine that can be converted to amide, sulfonamide, and tertiary amine derivatives in one step. The resulting reagents bear manifold functional groups, many of which would not be compatible with the original synthetic pathway. Exploiting this structural versatility and the known high reactivity toward thiols, the new-generation reagents were used in bioconjugation with an artificial retro-aldolase, containing an exposed cysteine and a reactive catalytic lysine. Whereas commercial reagents based on maleimide and iodoacetamide labeled both sites, the iodanes exclusively modified the cysteine residue. The study thus demonstrates that modular fluoroalkylation reagents can be used as tools for cysteine-selective bioconjugation.
- Václavík, Ji?í,Zschoche, Reinhard,Klimánková, Iveta,Matou?ek, Václav,Beier, Petr,Hilvert, Donald,Togni, Antonio
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supporting information
p. 6490 - 6494
(2017/05/15)
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- Heteroannulation enabled by a bimetallic Rh(III)/Ag(i) relay catalysis: Application in the total synthesis of aristolactam BII
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A redox-neutral bimetallic Rh(iii)/Ag(i) relay catalysis allowed the efficient construction of 3-alkylidene isoindolinones and 3-alkylidene isobenzofuranones. The Rh(iii) catalyst was responsible for the C-H monofluoroalkenylation reaction, whereas the Ag(i) salt was an activator for the follow-up cyclization. The methodology developed was applied as a key step in the rapid total synthesis of the natural product aristolactam BII.
- Ji, Wei-Wei,Lin,Li, Qingjiang,Wang, Honggen
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supporting information
p. 5665 - 5668
(2017/07/07)
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- Revisiting aryl amidine synthesis using metal amide and/or ammonia gas: Novel molecules and their biological evaluation
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Amidines, due to their unique biocompatibility and desirable physical characteristics, have been the functionality of choice as a scaffold for large number of drug synthesis. But still synthesis of amidines in the presence of other active functional groups or pharmacophore, remained a challenge. In this work, a simple and reliable protocol for conversion of nitrile-amide to unsubstituted amidine–amide is developed using metal amide and/or ammonia gas. The scope and efficiency of this synthetic strategy are demonstrated on several substrates which differ in functional groups will be discussed. In this process, 10 novel aryl amidines in good yields (upto 85%) were synthesized. Biological evaluation revealed that compound 4-(aminoiminomethyl)-N-(2-furanyl methyl) benzamide (IC50 = 9 μM) and 4-(aminoiminomethyl)-N-(3-pyridinylmethyl) benzamide (73.36% growth inhibition) showed moderate efficacy for cancer cells.
- Sahay, Ishani I.,Ghalsasi, Prasanna S.,Singh, Mala,Begum, Rasheedunnisa
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supporting information
p. 1400 - 1408
(2017/07/25)
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- Water-Proton Relaxivities of Radical Nanoparticles Self-Assembled via Hydration or Dehydration Processes
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Nanoparticles capable of accumulating in tumor tissues are promising materials for tumor imaging and therapy. In this study, two radical nanoparticles (RNPs), denoted as 1 and 2, composed of self-assembled ureabenzene derivatives possessing one or two amp
- Morishita, Kosuke,Okamoto, Yuna,Murayama, Shuhei,Usui, Kazuteru,Ohashi, Eriko,Hirai, Go,Aoki, Ichio,Karasawa, Satoru
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p. 7810 - 7817
(2017/08/15)
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- Transition-metal-free hydrogenation of aryl halides: From alcohol to aldehyde
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A transition-metal-and catalyst-free hydrogenation of aryl halides, promoted by bases with either aldehydes or alcohols, is described. One equivalent of benzaldehyde affords an equal yield as that of 0.5 equiv of benzyl alcohol. The kinetic study reveals that the initial rate of PhCHO is much faster than that of BnOH, in the ratio of nearly 4:1. The radical trapping experiments indicate the radical nature of this reaction. Based on the kinetic study, trapping and KIE experiments, and control experiments, a tentative mechanism is proposed. As a consequence, a wide range of (hetero)aryl iodides and bromides were efficiently reduced to their corresponding (hetero)arenes. Thus, for the first time, aldehydes are directly used as hydrogen source instead of other well-established alcohol-hydrogen sources.
- Zheng, Hong-Xing,Shan, Xiang-Huan,Qu, Jian-Ping,Kang, Yan-Biao
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supporting information
p. 5114 - 5117
(2017/11/07)
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- Palladium-Catalyzed, ortho-Selective C-H Halogenation of Benzyl Nitriles, Aryl Weinreb Amides, and Anilides
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A palladium-catalyzed, ortho-selective C-H halogenation methodology is reported herein. The highlight of the work is the highly selective C(sp2)-H functionalization of benzyl nitriles in the presence of activated C(sp3)-H bond, which results in good yields of the halogenated products with excellent regioselectivity. Along with benzyl nitriles, aryl Weinreb amides and anilides have been evaluated for the transformation using aprotic conditions. Mechanistic studies yield interesting aspects with respect to the pathway of the reaction and the directing group abilities.
- Das, Riki,Kapur, Manmohan
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p. 1114 - 1126
(2018/06/18)
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- Diastereoselective [3+2] Annulation of Aromatic/Vinylic Amides with Bicyclic Alkenes through Cobalt-Catalyzed C-H Activation and Intramolecular Nucleophilic Addition
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A highly diastereoselective method for the synthesis of dihydroepoxybenzofluorenone derivatives from aromatic/vinylic amides and bicyclic alkenes is described. This new transformation proceeds through cobalt-catalyzed C-H activation and intramolecular nucleophilic addition to the amide functional group. Transition-metal-catalyzed C-H activation reactions of secondary amides with alkenes usually lead to [4+2] or [4+1] annulation; to the best of our knowledge, this is the first time that a [3+2] cycloaddition is described in this context. The reaction proceeds under mild conditions and tolerates a wide range of functional groups. Mechanistic studies imply that the C-H bond cleavage may be the rate-limiting step. [3+2] instead of [4+2] or [4+1]: The diastereoselective [3+2] annulation of secondary amides with alkenes proceeds by cobalt-catalyzed C-H activation and intramolecular nucleophilic addition to the amide functional group under mild conditions. Mechanistic studies suggest that the C-H bond cleavage is the rate-limiting step.
- Gandeepan, Parthasarathy,Rajamalli, Pachaiyappan,Cheng, Chien-Hong
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supporting information
p. 4308 - 4311
(2016/04/01)
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- Rh(III)-Catalyzed Redox-Neutral Annulation of Primary Benzamides with Diazo Compounds: Approach to Isoquinolinones
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Reported herein is a Rh-catalyzed redox-neutral annulation of primary benzamides with diazo compounds, representing an efficient and economic protocol to isoquinolinones. The procedure exhibited good functional group tolerability, scalability, and regioselectivity, obviating the need for oxidants, and only environmentally benign N2 and H2O were released. Further utilization of the method provided an alternative route to functionalized isoquinolines.
- Wu, Youzhi,Sun, Peng,Zhang, Kaifan,Yang, Tie,Yao, Hequan,Lin, Aijun
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p. 2166 - 2173
(2016/03/15)
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- Ligand-Promoted Rh(III)-Catalyzed Coupling of Aryl C-H Bonds with Arylboron Reagents
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Rhodium(III)-catalyzed C-H arylation of arenes with phenylboronic acid pinacol esters has been achieved using a readily removable N-pentafluorophenylbenzamide directing group for the first time. The use of a bidentate phosphine ligand (Binap) significantly increased the yield of the cross-coupling of C-H bonds with organoboron reagents.
- Wang, Huai-Wei,Cui, Pei-Pei,Lu, Yi,Sun, Wei-Yin,Yu, Jin-Quan
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p. 3416 - 3422
(2016/05/19)
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- Palladium-Catalyzed Alkoxycarbonylation of Unactivated Secondary Alkyl Bromides at Low Pressure
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Catalytic carbonylations of organohalides are important C-C bond formations in chemical synthesis. Carbonylations of unactivated alkyl halides remain a challenge and currently require the use of alkyl iodides under harsh conditions and high pressures of CO. Herein we report a palladium-catalyzed alkoxycarbonylation of secondary alkyl bromides that proceeds at low pressure (2 atm CO) under mild conditions. Preliminary mechanistic studies are consistent with a hybrid organometallic-radical process. These reactions efficiently deliver esters from unactivated alkyl bromides across a diverse range of substrates and represent the first catalytic carbonylations of alkyl bromides with carbon monoxide.
- Sargent, Brendon T.,Alexanian, Erik J.
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supporting information
p. 7520 - 7523
(2016/07/06)
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- Mono- and triiodophenyl isocyanate as radiopacifying agents for methacrylate-based copolymers; Biocompatibility and non-toxicity
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New radiopaque acrylic copolymers were prepared via the copolymerization of methyl methacrylate (MMA) and acrylic acid (AA). The copolymers were made radiopaque through the reaction of carboxylic acid groups with 4-iodophenyl isocyanate and 3,4,5-triiodop
- Shiralizadeh, Saeed,Nasr-Isfahani, Hossein,Keivanloo, Ali,Bakherad, Mohammad
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p. 110400 - 110408
(2016/11/30)
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- Regiocontrolled Coupling of Aromatic and Vinylic Amides with α-Allenols to Form γ-Lactams via Rhodium(III)-Catalyzed C-H Activation
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A mild, regiocontrolled coupling of aromatic and vinylic amides with α-allenols to form γ-lactams via rhodium(III)-catalyzed C-H activation has been demonstrated. This [4 + 1] annulation reaction provides an efficient method for the synthesis of isoindolinones and 1,5-dihydro-pyrrol-2-ones bearing a tetrasubstituted carbon atom α to the nitrogen atom with good functional group tolerance. The hydroxyl group in the allene substrate is essential in controlling the chemo- and regioselectivity of the reaction probably by coordination interaction with the rhodium catalyst.
- Zhou, Zhi,Liu, Guixia,Lu, Xiyan
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supporting information
p. 5668 - 5671
(2016/11/17)
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- BODIPY-containing porous organic polymers for gas adsorption
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A series of BODIPY-containing microporous organic polymers was synthesized via a Sonogashira-Hagihara cross-coupling reaction of a BODIPY derivative with triple polymerisable groups and a range of aryl-alkyne monomers. All of the polymers show high isosteric heats of CO2 adsorption (23.3-27.3 kJ mol-1) because the incorporation of heteroatoms (N, B, F) from the BODIPY unit into the polymer skeleton enhanced the binding affinity between the pore wall and CO2 molecules. The aryl-alkyne monomer has a large influence on the surface area and CO2 adsorption performance of the resulting polymers. The polymer BDPCMP-3 shows a high Brunauer-Emmett-Teller specific surface area of up to 725 m2 g-1, while BDPCMP-2 with a low surface area of 582 m2 g-1 shows a high CO2 uptake ability of 2.25 mmol g-1 at 1.13 bar/273 K with a CO2/N2 adsorption selectivity of 32.3.
- Xu, Yunfeng,Chang, Dan,Feng, Shi,Zhang, Chong,Jiang, Jia-Xing
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supporting information
p. 9415 - 9423
(2016/11/11)
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- Rhodium(iii)-catalyzed C-H/C-C activation sequence: Vinylcyclopropanes as versatile synthons in direct C-H allylation reactions
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Succession of C-H activation and C-C activation was achieved by using a single rhodium(iii) catalyst. Vinylcyclopropanes were used as versatile coupling partners. Mechanistic studies suggest that the olefin insertion step is rate-determining and a facile β-carbon elimination is involved, which represents a novel ring opening mode of vinylcyclopropanes. This journal is
- Wu, Jia-Qiang,Qiu, Zhi-Ping,Zhang, Shang-Shi,Liu, Jing-Gong,Lao, Ye-Xing,Gu, Lian-Quan,Huang, Zhi-Shu,Li, Juan,Wang, Honggen
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supporting information
p. 77 - 80
(2015/01/09)
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- Cu(II)-catalyzed coupling of aromatic C-H bonds with malonates
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A new Cu(II)-catalyzed oxidative coupling of arenes with malonates has been developed using an amide-oxazoline directing group. The reaction proceeds via C(sp2)-H activation and malonate coupling, followed by intramolecular oxidative N-C bond formation. A variety of arenes bearing different substituents are shown to be compatible with this reaction.
- Wang, Hong-Li,Shang, Ming,Sun, Shang-Zheng,Zhou, Zeng-Le,Laforteza, Brian N.,Dai, Hui-Xiong,Yu, Jin-Quan
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supporting information
p. 1228 - 1231
(2015/03/14)
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- Ultrahigh Surface Area Zirconium MOFs and Insights into the Applicability of the BET Theory
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An isoreticular series of metal-organic frameworks (MOFs) with the ftw topology based on zirconium oxoclusters and tetracarboxylate linkers with a planar core (NU-1101 through NU-1104) has been synthesized employing a linker expansion approach. In this se
- Wang, Timothy C.,Bury, Wojciech,Gómez-Gualdrón, Diego A.,Vermeulen, Nicolaas A.,Mondloch, Joseph E.,Deria, Pravas,Zhang, Kainan,Moghadam, Peyman Z.,Sarjeant, Amy A.,Snurr, Randall Q.,Stoddart, J. Fraser,Hupp, Joseph T.,Farha, Omar K.
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supporting information
p. 3585 - 3591
(2015/03/30)
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- Copper-catalyzed semihydrogenation of alkynes to Z -alkenes
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Copper-catalyzed semihydrogenation of internal alkynes has been developed. The reaction proceeds under an atmosphere of hydrogen (5 atm) at 100 °C in the presence of a readily available [(PPh3)CuCl]4 catalyst to give various Z-alkenes stereoselectively.
- Semba, Kazuhiko,Kameyama, Ryohei,Nakao, Yoshiaki
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supporting information
p. 318 - 322
(2015/02/19)
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- Relative Rate Profiles of Functionalized Iodoarene Catalysts for Iodine(III) Oxidations
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A series of rate studies were conducted to evaluate the steric and electronic properties that govern the reactivity of iodoarene amide catalysts in the α-oxytosylation of propiophenone. A meta-substituted benzamide catalyst emerged as the most reactive. This catalyst was employed in the α-oxytosylation of a series of substituted propiophenones, returning the α-tosyloxy ketone products in excellent isolated yield.
- Lex, Timothy R.,Swasy, Maria I.,Whitehead, Daniel C.
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p. 12234 - 12243
(2016/01/09)
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- BENZAMIDE CGRP RECEPTOR ANTAGONISTS
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The present invention is directed to benzamide compounds which are antagonists of CGRP receptors and useful in the treatment or prevention of diseases in which CGRP is involved, such as migraine. The invention is also directed to pharmaceutical compositions comprising these compounds and the use of these compounds and compositions in the prevention or treatment of such diseases in which CGRP is involved.
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Page/Page column 55
(2015/11/09)
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- Compound
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Disclosed is a novel organic semiconductor material which has a twisted quaterphenylene skeleton as a central unit and simultaneously possesses a skeleton having an electron-transporting property and a skeleton having a hole-transporting property at the terminals of the quaterphenylene skeleton. Specifically, the organic semiconductor material has a [1,1′:2′,1″:2″,1′″]quaterphenyl-4-4′″-diyl group, and one of the terminals of the [1,1′:2′,1″:2″,1′″]quaterphenyl-4-4′″-diyl group is bonded to a skeleton having an electron-transporting property such as a benzoxazole group or an oxadiazole group. A skeleton having a hole-transporting property such as diarylamino group is introduced at the other terminal. This structure allows the formation of a compound having a bipolar property, a high molecular weight, an excellent thermal stability, a large band gap, and high triplet excitation energy.
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Paragraph 0542-0544
(2016/10/09)
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- OXIME DERIVATIVE, METHOD OF PRODUCING THE SAME AND INSECTICIDE COMPRISING THE SAME AS ACTIVE INGREDIENT
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PROBLEM TO BE SOLVED: To provide a compound having excellent insecticidal effect and useful as an active ingredient of an insecticide. SOLUTION: This invention provides an oxime derivative represented by general formula (1) (where Ra, X and n represent definitions described in the specifications) and an insecticide that comprises the same as an active ingredient. COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0215; 0217
(2018/10/03)
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