- Tuning thiol addition to squaraines by ortho-substitution and the use of serum albumin
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Tuning the reactivity of squaraine dyes toward nucleophilic addition of thiols was investigated. A series of water soluble, aniline-derived squaraines were synthesized with various ortho substitutions to the squaraine ring. As hypothesized, we found that placing moderately electron donating groups in the ortho position conveyed intermediate reactivity to thiols between the essentially non-reactive hydroxyl-substituted squaraines and very reactive non-substituted squaraines. Furthermore, serum albumin was tested for its influence on the addition of thiols to the squaraines. The dyes bind in the hydrophobic cavities of the protein, and thus we expected serum albumin to affect the squaraines' reactivity. Rather than a protective effect by the protein, we found a cooperative effect for thiol addition.
- Diehl, Katharine L.,Bachman, J. Logan,Anslyn, Eric V.
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Read Online
- Orthogonal Self-Assembly of a Two-Step Fluorescence-Resonance Energy Transfer System with Improved Photosensitization Efficiency and Photooxidation Activity
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During the past few decades, fabrication of multistep fluorescence-resonance energy transfer (FRET) systems has become one of the most attractive topics within supramolecular chemistry, chemical biology, and materials science. However, it is challenging t
- Jia, Pei-Pei,Xu, Lin,Hu, Yi-Xiong,Li, Wei-Jian,Wang, Xu-Qing,Ling, Qing-Hui,Shi, Xueliang,Yin, Guang-Qiang,Li, Xiaopeng,Sun, Haitao,Jiang, Yanrong,Yang, Hai-Bo
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supporting information
p. 399 - 408
(2021/01/12)
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- Synthesis of mitochondria-targeted coumarin-3-carboxamide fluorescent derivatives: Inhibiting mitochondrial TrxR2 and cell proliferation on breast cancer cells
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Targeting specific mitochondrial alterations to kill cancer cells without affecting their normal counterparts emerges as a feasible strategy. Coumarin derivatives have demonstrated the potential anti-breast cancer activities. By coupling coumarin-3-carbox
- Li, Yuanyuan,Tang, Qun,Xie, Yu,He, Dian,Yang, Kun,Zheng, Lifang
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supporting information
(2021/01/18)
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- Novel hybrid conjugates with dual estrogen receptor α degradation and histone deacetylase inhibitory activities for breast cancer therapy
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Hormone therapy targeting estrogen receptors is widely used clinically for the treatment of breast cancer, such as tamoxifen, but most of them are partial agonists, which can cause serious side effects after long-term use. The use of selective estrogen receptor down-regulators (SERDs) may be an effective alternative to breast cancer therapy by directly degrading ERα protein to shut down ERα signaling. However, the solely clinically used SERD fulvestrant, is low orally bioavailable and requires intravenous injection, which severely limits its clinical application. On the other hand, double- or multi-target conjugates, which are able to synergize antitumor activity by different pathways, thus may enhance therapeutic effect in comparison with single targeted therapy. In this study, we designed and synthesized a series of novel dual-functional conjugates targeting both ERα degradation and histone deacetylase inhibiton by combining a privileged SERD skeleton 7-oxabicyclo[2.2.1]heptane sulfonamide (OBHSA) with a histone deacetylase inhibitor side chain. We found that substituents on both the sulfonamide nitrogen and phenyl group of OBHSA unit had significant effect on biological activities. Among them, conjugate 16i with N-methyl and naphthyl groups exhibited potent antiproliferative activity against MCF-7 cells, and excellent ERα degradation activity and HDACs inhibitory ability. A further molecular docking study indicated the interaction patterns of these conjugates with ERα, which may provide guidance to design novel SERDs or PROTAC-like SERDs for breast cancer therapy.
- Zhao, Chenxi,Tang, Chu,Li, Changhao,Ning, Wentao,Hu, Zhiye,Xin, Lilan,Zhou, Hai-Bing,Huang, Jian
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- OXAZINE-BASED WATER-SOLUBLE FLUOROPHORE COMPOUNDS FOR IN VIVO NERVE IMAGING
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This invention provides novel oxazine-based, water soluble fluorophore compounds useful in in vivo nerve imaging, as well as compositions comprising them and methods for their use.
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- OXAZINE-BASED FLUOROPHORE COMPOUNDS FOR NERVE-SPECIFIC IMAGING
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This invention concerns novel oxazine-based fluorophore compounds useful in invivo nerve imaging, as well as compositions comprising them and methods for their use.
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- NEAR-INFRARED NERVE-SPARING FLUOROPHORES
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Provided are far red to near-infrared nerve-sparing fluorescent compounds, compositions comprising them, and methods of their use in medical procedures.
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- NERVE-SPECIFIC FLUOROPHORE FORMULATIONS FOR DIRECT AND SYSTEMIC ADMINISTRATION
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Nerve-specific fluorophore formulations for direct or systemic administration are described. The formulations can be used in fluorescence-guided surgery (FGS) to aid in nerve preservation during surgical interventions.
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- Hydrogenation and: N-Alkylation of anilines and imines via transfer hydrogenation with homogeneous nickel compounds
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The nickel-catalyzed N-Alkylation of a variety of arylamines via transfer hydrogenation in the absence of pressurized hydrogen and basic or acidic additives was achieved in a tandem reaction. This process was further extended to the CN bond reduction and N-Alkylation of a variety of imines with ethanol, the latter acting as a hydrogen and acetaldehyde source, which allowed for the reduction and subsequent condensation to yield the corresponding N-Alkylated products.
- Benitez-Medina, G. Eliad,García, Juventino J.
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supporting information
p. 17579 - 17587
(2019/12/23)
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- Cobalt-Catalyzed Reductive Alkylation of Amines with Carboxylic Acids
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Direct reductive alkylation of amines with carboxylic acid is carried out by using an inexpensive, air-stable cobalt/triphos catalytic system with molecular hydrogen as the reductant. This efficient synthetic method proceeds through reduction and condensation, followed by reduction of the in situ-generated imine into the amine in a green catalytic process.
- Emayavaramban, Balakumar,Chakraborty, Priyanka,Sundararaju, Basker
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p. 3089 - 3093
(2018/12/11)
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- 2,4-dinitrobenzenesulfonyl-containing coumarin compound and preparation method and application thereof
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The invention relates to a 2,4-dinitrobenzenesulfonyl-containing coumarin compound and a preparation method and an application thereof; a novel fluorescent molecular probe utilizes a specific reaction of sulfydryl and 2,4-dinitrobenzenesulfonyl and sensit
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Paragraph 0056
(2016/10/10)
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- Towards a general ruthenium-catalyzed hydrogenation of secondary and tertiary amides to amines
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A broad range of secondary and tertiary amides has been hydrogenated to the corresponding amines under mild conditions using an in situ catalyst generated by combining [Ru(acac)3], 1,1,1-tris(diphenylphosphinomethyl)ethane (Triphos) and Yb(OTf)3. The presence of the metal triflate allows to mitigate reaction conditions compared to previous reports thus improving yields and selectivities in the desired amines. The excellent isolated yields of two scale-up experiments corroborate the feasibility of the reaction protocol. Control experiments indicate that, after the initial reduction of the amide carbonyl group, the reaction proceeds through the reductive amination of the alcohol with the amine arising from collapse of the intermediate hemiaminal.
- Cabrero-Antonino, Jose R.,Alberico, Elisabetta,Junge, Kathrin,Junge, Henrik,Beller, Matthias
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p. 3432 - 3442
(2016/05/19)
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- Catalytic N-Alkylation of Amines Using Carboxylic Acids and Molecular Hydrogen
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A convenient, practical and green N-alkylation of amines has been accomplished by applying readily available carboxylic acids in the presence of molecular hydrogen. Applying an in situ formed ruthenium/triphos complex and an organic acid as cocatalyst, a broad range of alkylated secondary and tertiary amines are obtained in good to excellent yields. This novel method is also successfully applied for the synthesis of unsymmetrically substituted N-methyl/alkyl anilines through a direct three-component coupling reaction of the corresponding amines, carboxylic acids, and CO2 as a C1 source.
- Sorribes, Iván,Cabrero-Antonino, Jose R.,Vicent, Cristian,Junge, Kathrin,Beller, Matthias
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supporting information
p. 13580 - 13587
(2015/11/10)
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- Palladium-Catalyzed Amination of N-Free 2-Chloro-7-azaindole
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A simple and efficient procedure for the Pd-catalyzed amination of N-free 2-chloro-7-azaindole is described, using either primary or secondary amines. An optimized combination of Brettphos, a Brettphos precatalyst, and LiHMDS in THF led us to a novel methodology, applied to various functionalized amines to study the scope of the reaction. This is the first report of cross-coupling amination on N-free 2-chloro-7-azaindole.
- Plas, Aurélie,Martin, Camille,Joubert, Nicolas,Viaud-Massuard, Marie-Claude
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supporting information
p. 4710 - 4713
(2015/10/12)
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- Thiol activated prodrugs of sulfur dioxide (SO2) as MRSA inhibitors
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Drug resistant infections are becoming common worldwide and new strategies for drug development are necessary. Here, we report the synthesis and evaluation of 2,4-dinitrophenylsulfonamides, which are donors of sulfur dioxide (SO2), a reactive sulfur species, as methicillin-resistant Staphylococcus aureus (MRSA) inhibitors. N-(3-Methoxyphenyl)-2,4-dinitro-N-(prop-2-yn-1-yl)benzenesulfonamide (5e) was found to have excellent in vitro MRSA inhibitory potency. This compound is cell permeable and treatment of MRSA cells with 5e depleted intracellular thiols and enhanced oxidative species both results consistent with a mechanism involving thiol activation to produce SO2.
- Pardeshi, Kundansingh A.,Malwal, Satish R.,Banerjee, Ankita,Lahiri, Surobhi,Rangarajan, Radha,Chakrapani, Harinath
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p. 2694 - 2697
(2015/06/08)
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- Rational design of biotinylated probes: Fluorescent turn-on detection of (strept)avidin and bioimaging in cancer cells
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Two fluorescent probes SPS1 and SPS2 were designed by connecting biotin to an environment-sensitive coumarin fluorophore. Streptavidin and avidin induced dramatical fluorescence changes in both probes. SPS2 has potential in fluorescent imaging of biotin r
- Sun, Qian,Qian, Junhong,Tian, Haiyu,Duan, Liping,Zhang, Weibing
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supporting information
p. 8518 - 8521
(2014/07/22)
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- INDAZOLEPROPIONIC ACID AMIDE COMPOUND
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Disclosed is a compound which is useful in preventing and treating cardiac arrhythmia such as atrial fibrillation. A compound represented by formula (1) or a pharmaceutically acceptable salt of the same. In formula (1), ring X represents benzene or pyridine; R1 represents an optionally substituted alkyl group; R2 represents an optionally substituted aryl group, an optionally substituted heterocyclic group, an optionally substituted arylalkyl group or an optionally substituted heterocyclic group-substituted alkyl group; R3, R4, R5, R6, R7, R8 and R9 represent each hydrogen or an alkyl group, provided that R3 and R5 may be bonded to each other to form, together with the carbon atom adjacent thereto, a cycloalkyl group; and m represents 0 or 1.
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Page/Page column 38-39
(2012/02/01)
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- Assembly of substituted 2-alkylquinolines by a sequential palladium-catalyzed Ci-N and Ci-C bond formation
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Diversity: A range of substituted 2-alkylquinolines can be prepared in a general and efficient synthetic approach that employs mild reaction conditions (see scheme). The synthesis is based on a sequential palladium-catalyzed Ci-N and Ci-C bond formation, followed by palladium-catalyzed aromatization, and results in the formation of the desired compounds in one step. Copyright
- Matsubara, Yoshio,Hirakawa, Saori,Yamaguchi, Yoshihiro,Yoshida, Zen-Ichi
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experimental part
p. 7670 - 7673
(2011/10/05)
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- Rhodamine spiroamides for multicolor single-molecule switching fluorescent nanoscopy
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The design, synthesis, and evaluation of new rhodamine spiroamides are described. These molecules have applications in optical nanoscopy based on random switching of the fluorescent single molecules. The new markers may be used in (co)localization studies of various objects and their (mutual) positions and shape can be determined with a precision of a few tens of nanometers. Multicolor staining, good photoactivation, a large number of emitted photons, and selective chemical binding with amino or thiol groups were achieved due to the presence of various functional groups on the rhodamine spiroamides. Rigidized sulfonated xanthene fragment fused with six-membered rings, N,N′-bis(2,2,2-trifluoroethyl) groups, and a combination of additional double bonds and sulfonic acid groups with simple aliphatic spiroamide residue provide multicolor properties and improve performance of the rhodamine spiroamides in photoactivation and bioconjugation reactions. Having both essential parts of the photoswitchable assembly - the switching and the fluorescent (reporter) groups - combined in one chemical entity make this approach attractive for further development. A series of rhodamine spiroamides is presented along with characterizations of their most relevant properties for application as fluorescent probes in single-molecule switching and localization microscopy. Optical images with resolutions on the nanometer scale illustrate the potential of the labels in the colocalization of biological objects and the two-photon activation technique with optical sectioning.
- Belov, Vladimir N.,Bossi, Mariano L.,Foelling, Jonas,Boyarskiy, Vadim P.,Hell, Stefan W.
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experimental part
p. 10762 - 10776
(2010/04/05)
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- Reductive monoalkylation of nitro aryls in one-pot
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The scope of the serendipitous reductive monoalkylation of ethyl (4-methoxy-3-nitrophenyl) acetate taking place during reduction of the nitro functionality to the corresponding primary amine when treated with hydrogen (1 atm) over Pd/C (10%) in ethanol is investigated. Upon prolonged reaction time the reaction conducted in ethanol and methanol yields significant amount of the corresponding secondary amines, while when performed in n-butanol and i-propanol it only resulted in the formation of a small amount of the corresponding secondary amines. Further development of the reductive monoalkylation reaction provided conditions that facilitate conversion of a range of different nitro aryls in one-pot to the corresponding secondary benzyl amino aryls in mostly good to excellent yields. This is accomplished by using hydrogen (1 atm) over Pd/C (10%) as reducing agent and benzaldehyde as the benzyl source combined with a stepwise reaction sequence. This chemistry was further extended to the formation of substituted benzyl amino aryls. The yields of the latter products varied dramatically depending on the substitution patterns associated with the benzaldehyde. However, by altering the reaction conditions it was possible to improve the yields of the benzylated products.
- Sydnes, Magne O.,Kuse, Masaki,Isobe, Minoru
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p. 6406 - 6414
(2008/09/21)
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- One-pot reductive monoalkylation of nitro aryls with hydrogen over Pd/C
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A range of different nitro aryls were converted in one-pot to the corresponding secondary alkyl amino aryls in good to excellent yields by using aldehydes as alkyl source and hydrogen over Pd/C (10%) as reducing agent. In all examples, but one, the second
- Sydnes, Magne O.,Isobe, Minoru
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p. 1199 - 1202
(2008/09/17)
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- Reductive monoalkylation of aromatic and aliphatic nitro compounds and the corresponding amines with nitriles
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(Chemical Equation Presented) A simple, selective, rapid, and efficient procedure for the synthesis of secondary amines from the reductive alkylation of either aliphatic or aromatic nitro compounds and the corresponding amines is reported. Ammonium formate is used as the hydrogen source and Pd/C as the hydrogen transfer catalyst. The reaction is carried out at room temperature. The rate differences for the preferential formation of secondary over tertiary products are due to both steric and electronic factors.
- Nacario, Ruel,Kotakonda, Shailaja,Fouchard, David M. D.,Tillekeratne, L. M. Viranga,Hudson, Richard A.
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p. 471 - 474
(2007/10/03)
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- Synthesis of novel thrombin inhibitors. Use of ring-closing metathesis reactions for synthesis of P2 cyclopentene- and cyclohexenedicarboxylic acid derivatives
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The thrombin inhibitory tripeptide D-Phe-Pro-Arg has been mimicked using either cyclopentenedicarboxylic derivatives or a cyclohexenedicarboxylic derivative as surrogate for the P2 proline. In the P3 position, tertiary amides were optimized as D-Phe P3 re
- Thorstensson, Fredrik,Kvarnstr?m, Ingemar,Musil, Djordje,Nilsson, Ingemar,Samuelsson, Bertil
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p. 1165 - 1179
(2007/10/03)
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