- Cell-Trappable BODIPY-NBD Dyad for Imaging of Basal and Stress-Induced H2S in Live Biosystems
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H2S is a gaseous signaling molecule that is involved in many physiological and pathological processes. In general, the level of intracellular H2S (1 μM) is much lower than that of GSH (~1–10 mM), leading to the remaining challenge o
- Huang, Haojie,Ji, Xiuru,Jiao, Yan,Pang, Zhili,Sun, Lu,Tang, Xinjing,Tu, Xiaoqiang,Xi, Zhen,Ye, Haishun,Yi, Long
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p. 1733 - 1741
(2022/02/05)
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- Indium-Catalyzed C?F Bond Transformation through Oxymetalation/β-Fluorine Elimination to Access Fluorinated Isocoumarins
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Fluorinated heterocycles have attracted much attention in the pharmaceutical and agrochemical industries. Many strategies have already been developed to achieve the synthesis of fluorinated heterocycles. Formidable challenges remain, however, in the synthesis of fluorinated isocoumarin derivatives that are among the most alluring structural motifs. Herein, the indium-catalyzed C?F bond transformation of 2-(2,2-difluorovinyl) benzoates is reported, which are readily accessible compounds, to give a diverse array of fluorinated isocoumarins. The present reaction proceeds smoothly using inexpensive reagents: a catalytic amount of indium salt in the presence of zinc salt. A theoretical calculation of potential energy profiles showed that the reaction consists of oxymetalation with the elimination of alkyl halide and the β-fluorine elimination.
- Yata, Tetsuji,Nishimoto, Yoshihiro,Chiba, Kouji,Yasuda, Makoto
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supporting information
p. 8288 - 8294
(2021/05/21)
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- Cu-Catalyzed C-H Alkenylation of Benzoic Acid and Acrylic Acid Derivatives with Vinyl Boronates
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An efficient Cu-catalyzed C-H alkenylation with acyclic and cyclic vinyl boronates was realized for the first time under mild conditions. The scope of the vinyl borons and the compatibility with functional groups including heterocycles are superior than Pd-catalyzed C-H coupling with vinyl borons, providing a reliable access to multisubstituted alkenes and dienes. Subsequent hydrogenation of the product from the internal vinyl borons will lead to installation of secondary alkyls.
- Li, Jian-Jun,Wang, Cheng-Gang,Yu, Jin-Feng,Wang, Peng,Wang, Peng,Yu, Jin-Quan
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p. 4692 - 4696
(2020/06/25)
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- SUBSTITUTED 1,1'-BIPHENYL COMPOUNDS, ANALOGUES THEREOF, AND METHODS USING SAME
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The present invention includes substituted 3,3'-bis(phenoxymethyl)-1,1'-biphenyl compounds, analogues thereof, and compositions comprising the same, that can be used to treat or prevent hepatitis B virus (HBV) and/or hepatitis D virus (HDV) infections in a patient.
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Page/Page column 41
(2019/10/23)
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- Sterically Shielded, Stabilized Nitrile Imine for Rapid Bioorthogonal Protein Labeling in Live Cells
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In pursuit of fast bioorthogonal reactions, reactive moieties have been increasingly employed for selective labeling of biomolecules in living systems, posing a challenge in attaining reactivity without sacrificing selectivity. To address this challenge, here we report a bioinspired strategy in which molecular shape controls the selectivity of a transient, highly reactive nitrile imine dipole. By tuning the shape of structural pendants attached to the ortho position of the N-aryl ring of diaryltetrazoles-precursors of nitrile imines, we discovered a sterically shielded nitrile imine that favors the 1,3-dipolar cycloaddition over the competing nucleophilic addition. The photogenerated nitrile imine exhibits an extraordinarily long half-life of 102 s in aqueous medium, owing to its unique molecular shape that hinders the approach of a nucleophile as shown by DFT calculations. The utility of this sterically shielded nitrile imine in rapid (~1 min) bioorthogonal labeling of glucagon receptor in live mammalian cells was demonstrated.
- An, Peng,Lewandowski, Tracey M.,Erbay, Tug?e G.,Liu, Peng,Lin, Qing
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p. 4860 - 4868
(2018/04/16)
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- Chiral 3-substituted isoindolinone compounds, and preparation method and application thereof
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The invention discloses chiral 3-substituted isoindolinone compounds, and a preparation method and application thereof. The compounds are as shown in a formula I which is described in the specification. The preparation method comprises a step of subjecting a compound as shown in a formula II and a compound as shown in a formula III to a Ugi two-component four-center reaction or subjecting a compound as shown in a formula IV, a compound as shown in a formula V and the compound as shown in the formula III to a Ugi three-component four-center reaction in the presence of a chiral phosphoric acid catalyst so as to obtain the compounds as shown in the formula I after completion of the reactions. According to the invention, extensively available raw materials and the cheap and easily available chiral catalyst are used; the raw materials are subjected to the Ugi two-component four-center reaction or the Ugi three-component four-center reaction so as to efficiently prepare the chiral 3-substituted isoindolinone compounds in one step; reaction conditions are mild; and the prepared compounds are stable in the air, high in yield, good in enantioselectivity and easy to separate and purify, and have good application prospects.
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Paragraph 0058-0067; 0082; 0083; 0084; 0085; 0086-0090
(2017/09/01)
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- TiCl4-Mediated Preparation of Thiophthalide Derivatives via Formal Thio-Passerini Reactions
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By the formal extension of the Passerini reaction to thiocarbonyl derivatives, the straightforward preparation of thiophthalides is disclosed. This method involves the intermediate formation of a sulfanyl-phthalide and a titanium tetrachloride mediated is
- Ponra, Sudipta,Nyadanu, Aude,Ka?m, Laurent El,Grimaud, Laurence,Vitale, Maxime R.
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p. 4060 - 4063
(2016/08/30)
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- Highly enantioselective synthesis of 2,3-dihydro-1 H-imidazo[2,1-a isoindol-5(9b H)-ones via catalytic asymmetric intramolecular cascade imidization-nucleophilic addition-lactamization
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Highly enantioselective catalytic asymmetric intramolecular cascade imidization-nucleophilic addition-lactamization of N1-alkylethane-1,2-diamine with methyl 2-formylbenzoate catalyzed by a chiral phosphoric acid represents the first efficient method for the preparation of medicinally interesting chiral 2,3-dihydro-1H-imidazo[2,1-a]isoindol-5(9bH)-ones with high yields and excellent enantioselectivities. This strategy has been shown to be quite general toward various methyl 2-formylbenzoates.
- He, Yuwei,Cheng, Chuyu,Chen, Bin,Duan, Kun,Zhuang, Yue,Yuan, Bo,Zhang, Meisan,Zhou, Yougui,Zhou, Zihong,Su, Yu-Jun,Cao, Rihui,Qiu, Liqin
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supporting information
p. 6366 - 6369
(2015/01/16)
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- A synthetic route to chiral C(3)-functionalized phthalides via a Ag(I)-catalyzed allylation/transesterification sequence
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A Ag(I)-catalyzed synthesis of chiral C(3)-substituted phthalides (8a-f) via a Sakurai-Hosomi allylation/transesterification reaction is described (ee ≤86%). A notable feature of this reaction is that it utilizes ortho-substituted aldehydes, which are a class of compounds that generally afford poor levels of stereoinduction when applying most known catalytic asymmetric allylation approaches. It was also found that elongation of the n-alkyl chain length (R1, up to n=6; R2=H) of the starting alkyl 2-formylbenzoates (7g-i) improved the enantiomeric excess (ee) of the product.
- Mirabdolbaghi, Roya,Dudding, Travis
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p. 3287 - 3292
(2013/04/24)
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- DIBENZOCYCLOHEPTATONE DERIVATIVES AND PHARMACEUTICAL AGENTS CONTAINING SAID COMPOUNDS
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The present invention relates to compounds of the formula I wherein R1, R2, R3, R4, X and Y have the meanings given in the description. The compounds have an action which is immunomodulating and inhibits or regulates the release of IL-1β and/or TNF-α. The
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- Design, Synthesis, and biological evaluation of novel disubstituted dibenzosuberones as highly potent and selective inhibitors of p38 mitogen activated protein kinase
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Synthesis, biological testing, structure-activity relationships (SARs), and selectivity of novel disubstituted dibenzosuberone derivatives as p38 MAP kinase inhibitors are described. Hydrophilic moieties were introduced at the 7-, 8-, and 9-position of th
- Koeberle, Solveigh C.,Fischer, Stefan,Schollmeyer, Dieter,Schattel, Verena,Grütter, Christian,Rauh, Daniel,Laufer, Stefan A.
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p. 5868 - 5877
(2012/08/27)
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- BENZIMIDAZOLE INHIBITORS OF LEUKOTRIENE PRODUCTION
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The present invention relates to compounds of formula IA and IB and pharmaceutically acceptable salts thereof, wherein R1-R7 are as defined herein. The invention also relates to pharmaceutical compositions comprising these compounds,
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Page/Page column 50
(2012/05/19)
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- An indium-mediated allylative/transesterification DFT-directed approach to chiral C(3)-functionalized phthalides
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A one-pot synthesis of chiral C(3)-substituted phthalides via an indium-mediated allylation/transesterification reaction is described. The development of this reaction was facilitated through the applied use of DFT calculations to rationalize the stereoselection of a chiral In-mediated process. It was discovered that the enantiomeric excess of this reaction depended upon the steric size, chain length, and substitution of the aldehyde employed.
- Mirabdolbaghi, Roya,Dudding, Travis
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supporting information; experimental part
p. 3748 - 3751
(2012/09/07)
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- Synthesis of chiral 3-substituted phthalides by a sequential organocatalytic enantioselective aldol-lactonization reaction. Three-step synthesis of (S)-(-)-3-butylphthalide
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(Chemical Equation Presented) The development of efficient methods for the facile construction of important molecular frameworks is an important goal in organic synthesis. Chiral 3-substituted phthalides are widely distributed in a large collection of natural products with broad, potent, and potentially path-pointing biological activities. In this investigation, we have uncovered an unprecedented organocatalytic asymmetric aldol-lactonization reaction of 2-formylbenzoic esters with ketones/aldehydes for convenient construction of the enantioenriched "privileged" scaffold. As a result of the sensitive nature of substrate structures of an organocatalytic enantioselective aldol reaction, after extensive optimization of reaction conditions, catalyst L-prolinamide alcohol IV is identified as the best promoter. Interestingly, it is found that in this reaction, addition of an acid additive PhCO2H can significantly enhance reaction efficiency with use of only as low as 2.5 mol % IV for the process. Moreover, due to the sensitivity of reaction conditions toward a sequential aldol-lactonization process without affecting enantioselectivity and racemization, it is essential to remove the catalyst for the subsequent facile lactonization reaction in the presence of K 2CO3. The aldol-lactonization processes serve as a powerful approach to the preparation of synthetically and biologically important 3-substitued phthalides with a high level of enantioselectivities. A 3-step catalytic asymmetric synthesis of the natural product of 3-butylphthalide is reported.
- Zhang, Haoyi,Zhang, Shilei,Liu, Lu,Luo, Guangshun,Duan, Wenhu,Wang, Wei
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supporting information; experimental part
p. 368 - 374
(2010/03/30)
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- A facile enantioselective synthesis of the dimeric pyranonaphthoquinone core of the cardinalins
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The enantioselective synthesis of a dimeric pyranonaphthoquinone closely related to cardinalin 3 is described. Key steps include the Hauser-Kraus annulation between a cyanophthalide and a chiral enone to create the naphthalene skeleton, a Suzuki-Miyaura h
- Brimble, Margaret A.,Gibson, Jennifer S.,Sejberg, Jimmy J. P.,Sperry, Jonathan
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p. 867 - 870
(2008/12/22)
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- Enantioselective synthesis of the dimeric pyranonaphthoquinone core of the cardinalins using a late-stage homocoupling strategy
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The enantioselective synthesis of a dimeric pyranonaphthoquinone closely related to the cardinalins is described. Whilst attempts to effect a double Hauser-Kraus annulation of enone 5 were unsuccessful using both bis-phthalide 4 and bis-sulfone 21, a sing
- Sperry, Jonathan,Gibson, Jennifer S.,Sejberg, Jimmy J. P.,Brimble, Margaret A.
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supporting information; experimental part
p. 4261 - 4270
(2009/02/07)
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- Furan ring opening - Isocoumarine ring closure: A recyclization reaction of 2-carboxyaryldifurylmethanes
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A general method for the synthesis of isocoumarine derivatives has been developed. Bis(5-R-2-furyl)methylbenzoic acids (R = methyl, ethyl) underwent recyclization and subsequent cyclization into tetracyclic isochromene-1-one derivatives under treatment with hydrogen chloride in methanol. It has been shown that intermediate 4-(5-R-furan-2-yl)-3-(3-oxo-3-R-propyl)-isochromene-1- ones can be obtained selectively by varying a concentration of the hydrogen chloride and reaction times. In the case of R = tert-butyl only corresponding 4-[5-(tert-butyl)-2-furyl]-3-(4,4-dimethyl-3-oxopentyl)-1-isochromenones were isolated regardless of the reaction conditions.
- Abaev, Vladimir T.,Dmitriev, Artem S.,Gutnov, Andrey V.,Podelyakin, Sergey A.,Butin, Alexander V.
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p. 1195 - 1204
(2007/10/03)
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- Reactions of carbonyl compounds in basic solutions. Part 24. 1 The mechanism of the base-catalysed ring fission of substituted benzocyclobutene-1,2-diones
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The rate coefficients for the base-catalysed ring fission of a series of substituted benzocyclobutenediones to give the corresponding 2-formylbenzoic acids have been determined in water at 25.0 and 60.0°C. The effects of 4-substituents and 4,5-di-substituents on the rates have been correlated using a modified Hammett equation to give a reaction constant, ρ, equal to ca. 3.6 at 25.0°C. The activation parameters have been calculated. The effect of solvent composition on the rates has been studied. The kinetic solvent isotope effect, product composition and enrichment in 18O-enriched water have also been studied. All the evidence indicates a mechanistic pathway which proceeds by rapid reversible addition of hydroxide anion to the dione, followed by intramolecular nucleophilic attack on the second carbonyl group and formation of a carbanionic intermediate.
- Bowden, Keith,Horri, M. Vahid
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p. 989 - 992
(2007/10/03)
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