- Synthesis and characterization of optically active cyclic 6,6'-dinitro-1,1-binaphthyl-2,2'-diethers
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A series of racemic and enantiomerically pure 6,6'-dinitro-1,1'-binaphthyl 2,2'-diethers 1 have been synthesized by the nitration of the corresponding cyclic ethers and both the reactivity of nitration and the (chir)optical properties proved to be very sensitive for the chain length of the ether bridge.
- Van Es,Biemans,Meijer
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- Synthesis and stereochemical properties of chiral hetero[7]helicenes structured by a benzodiheterole ring core
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A new hetero[7]helicene 1NN structured by a diazabenzodiheterole (pyrroloindole) ring core was successfully synthesized by catalytic domino cyclodehydrogenation with Pd(OAc)2 and O2 as the key step. Significantly, 1NN was stereochemically stable at room temperature and could be subjected to optical resolution by chiral HPLC. Furthermore, kinetic analysis of 1NN and DFT calculations on its variants revealed that the stereo-chemical stability of the benzodiheterole-based helicenes was highly dependent on not only the heteroaromatic ring component but also on the N-substituent of the pyrrole ring unit.
- Arae, Sachie,Mori, Takaaki,Kawatsu, Takahiro,Ueda, Daiki,Shigeta, Yusuke,Hamamoto, Nobutsugu,Fujimoto, Hitoshi,Sumimoto, Michinori,Imahori, Tatsushi,Igawa, Kazunobu,Tomooka, Katsuhiko,Punniyamurthy, Tharmalingam,Irie, Ryo
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- Evaluation of the stability of cucurbit[8]uril-based ternary host?guest complexation in physiological environment and the fabrication of a supramolecular theranostic nanomedicine
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Background: Supramolecular theranostics have exhibited promising potentials in disease diagnosis and therapy by taking advantages of the dynamic and reversible nature of non-covalent interactions. It is extremely important to figure out the stability of the driving forces in physiological environment for the preparation of theranostic systems. Methods: The host?guest complexation between cucurbit[8]uril (CB[8]), 4,4′-bipyridinium, and napththyl guest was fully studied using various characterizations, including nuclear magnetic resonance spectroscopy, ultraviolet–visible (UV–vis) spectroscopy, isothermal titration calorimetry (ITC). The association constants of this ternary complex were determined using isothermal titration calorimetry. The stability of the non-covalent interactions and self-assemblies form from this molecular recognition was confirmed by UV–vis spectroscopy and dynamic light scattering (DLS). A supramolecular nanomedicine was constructed on the basis of this 1:1:1 ternary recognition, and its in vitro and in vivo anticancer efficacy were thoroughly evaluated. Positron emission tomography (PET) imaging was used to monitor the delivery and biodistribution of the supramolecular nanomedicine. Results: Various experiments confirmed that the ternary complexation between 4,4′-bipyridinium, and napththyl derivative and CB[8] was stable in physiological environment, including phosphate buffered solution and cell culture medium. Supramolecular nanomedicine (SNM@DOX) encapsulating a neutral anticancer drug (doxrubincin, DOX) was prepared based on this molecular recognition that linked the hydrophobic poly(ε-caprolactone) chain and hydrophilic polyethylene glycol segment. The non-covalent interactions guaranteed the stability of SNM@DOX during blood circulation and promoted its tumor accumulation by taking advantage of the enhanced permeability and retention effect, thus greatly improving the anti-tumor efficacy as compared with the free drug. Conclusion: Arising from the host-enhanced charge-transfer interactions, the CB[8]-based ternary recognition was stable enough in physiological environment, which was suitable for the fabrication of supramolecular nanotheranostics showing promising potentials in precise cancer diagnosis and therapy. Graphic Abstract: [Figure not available: see fulltext.].
- Wu, Han,Chen, Zuobing,Qi, Shaolong,Bai, Bing,Ye, Jiajun,Wu, Dan,Shen, Jie,Kang, Fei,Yu, Guocan
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- Enantioselective Construction of Axially Chiral Amino Sulfide Vinyl Arenes by Chiral Sulfide-Catalyzed Electrophilic Carbothiolation of Alkynes
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The enantioselective construction of axially chiral compounds by electrophilic carbothiolation of alkynes is disclosed for the first time. This enantioselective transformation is enabled by the use of a Ts-protected bifunctional sulfide catalyst and Ms-protected ortho-alkynylaryl amines (Ts=tosyl; Ms=mesyl). Both electrophilic arylthiolating and electrophilic trifluoromethylthiolating reagents are suitable for this reaction. The obtained products of axially chiral vinyl–aryl amino sulfides can be easily converted into biaryl amino sulfides, biaryl amino sulfoxides, biaryl amines, vinyl–aryl amines, and other valuable difunctionalized compounds.
- Ji, Jieying,Jiang, Quanbin,Liang, Yaoyu,Luo, Jie,Zhang, Xiaoyan,Zhao, Xiaodan
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supporting information
p. 4959 - 4964
(2020/02/11)
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- Deacetylative Amination of Acetyl Arenes and Alkanes with C-C Bond Cleavage
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The Br?nsted acid-catalyzed synthesis of primary amines from acetyl arenes and alkanes with C-C bond cleavage is described. Although the conversion from an acetyl group to amine has traditionally required multiple steps, the method described herein, which uses an oxime reagent as an amino group source, achieves the transformation directly via domino transoximation/Beckmann rearrangement/Pinner reaction. The method was also applied to the synthesis of γ-aminobutyric acids, such as baclophen and rolipram.
- Hyodo, Kengo,Hasegawa, Genna,Maki, Hiroya,Uchida, Kingo
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supporting information
p. 2818 - 2822
(2019/04/25)
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- PRODUCTION METHOD OF PRIMARY AMINE COMPOUND
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PROBLEM TO BE SOLVED: To provide a simple production method of a primary amine compound unnecessary for complicated procedures and toxic sodium azide or the like. SOLUTION: A production method of a primary amine compound includes a step for reacting a ketone compound and an oxime compound in the presence of alcohol and an acid catalyst. Preferably, the acid catalyst is hydrochloric acid, sulfuric acid, methanesulfonic acid, camphorsulfonic acid, a tosyl acid hydrate, trifluoromethane sulfonic acid or a boron trifluoride diethyl ether complex. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0026; 0027; 0029
(2019/09/20)
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- AMINATION AND HYDROXYLATION OF ARYLMETAL COMPOUNDS
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In one aspect, the present disclosure provides methods of preparing a primary or secondary amine and hydroxylated aromatic compounds. In some embodiments, the aromatic compound may be unsubstituted, substituted, or contain one or more heteroatoms within the rings of the aromatic compound. The methods described herein may be carried out without the need for transition metal catalysts or harsh reaction conditions.
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Paragraph 0098; 0134; 0135; 0147
(2018/03/25)
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- NOVEL ORGANIC COMPOUND, NEAR-INFRARED FLUORESCENT CONSTANT MEDIUM CONTAINING SAME, AND METHOD FOR NANO-GRANULATING CONSTANT MEDIUM
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The present invention relates to a novel organic compound, a near-infrared fluorescent constant medium containing the same, and a method for nano-granulating the constant medium.
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Paragraph 0109; 0110; 0111
(2018/12/04)
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- Rapid heteroatom transfer to arylmetals utilizing multifunctional reagent scaffolds
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Arylmetals are highly valuable carbon nucleophiles that are readily and inexpensively prepared from aryl halides or arenes and widely used on both laboratory and industrial scales to react directly with a wide range of electrophiles. Although C-C bond formation has been a staple of organic synthesis, the direct transfer of primary amino (-NH2) and hydroxyl (-OH) groups to arylmetals in a scalable and environmentally friendly fashion remains a formidable synthetic challenge because of the absence of suitable heteroatom-transfer reagents. Here, we demonstrate the use of bench-stable N-H and N-alkyl oxaziridines derived from readily available terpenoid scaffolds as efficient multifunctional reagents for the direct primary amination and hydroxylation of structurally diverse aryl- and heteroarylmetals. This practical and scalable method provides one-step synthetic access to primary anilines and phenols at low temperature and avoids the use of transition-metal catalysts, ligands and additives, nitrogen-protecting groups, excess reagents and harsh workup conditions.
- Gao, Hongyin,Zhou, Zhe,Kwon, Doo-Hyun,Coombs, James,Jones, Steven,Behnke, Nicole Erin,Ess, Daniel H.,Kürti, László
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p. 681 - 688
(2017/06/30)
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- Nickel-Catalyzed Amination of Aryl Carbamates with Ammonia
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Aryl carbamates were employed in the nickel-catalyzed monoarylation of ammonia. The applied, well-defined single-component nickel(II) precatalyst contains a Josiphos ligand, is air-stable, and operates without any ancillary reductant. This catalyst system
- Schranck, Johannes,Furer, Patrick,Hartmann, Veronika,Tlili, Anis
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supporting information
p. 3496 - 3500
(2017/07/04)
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- Catalytic Ester and Amide to Amine Interconversion: Nickel-Catalyzed Decarbonylative Amination of Esters and Amides by C?O and C?C Bond Activation
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An efficient nickel-catalyzed decarbonylative amination reaction of aryl and heteroaryl esters has been achieved for the first time. The new amination protocol allows the direct interconversion of esters and amides into the corresponding amines and represents a good alternative to classical rearrangements as well as cross coupling reactions.
- Yue, Huifeng,Guo, Lin,Liao, Hsuan-Hung,Cai, Yunfei,Zhu, Chen,Rueping, Magnus
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supporting information
p. 4282 - 4285
(2017/04/03)
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- Synthesis and cycloxygenase inhibitory properties of new naphthalene-methylsulfonamido, naphthalene-methylsulfonyl and tetrahydronaphthalen-methylsulfonamido compounds
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We synthesized a series of new naphthalene derivatives: naproxen- and 6-methoxy naphthalene acetic acid-like 1-5. In these compounds the carboxylic function, typical of the classical NSAIDs, was replaced by a methylsulfonamido (1, 2 and 6a-c) or methylsulfonyl (3-5) group present in some selective COX-2 inhibitors. We also synthesized compounds 7 and 8 in which the naphthalene portion was substituted by tetrahydronaphthalene ring. Some of the new compounds were assayed for their enzymatic inhibitory activity towards cycloxygenase enzymes. Compounds 4 and 6b, at a concentration of 10 μM exhibit percentage inhibition values of 65%, 50% and 29%, 87% towards COX-2 and COX-1, respectively. The substitution of carboxylic group with a mehylsulfonamido or a methylsulfonyl groups does not allow to direct the selectivity versus to cycloxygenase enzymes.
- Nencetti, Susanna,Ciccone, Lidia,Rossello, Armando,Nuti, Elisa,Milanese, Claudio,Orlandini, Elisabetta
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p. 406 - 412
(2015/07/27)
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- Monna, a potent and selective blocker for transmembrane protein with unknown function 16/anoctamin-1
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Transmembrane protein with unknown function 16/anoctamin-1 (ANO1) is a protein widely expressed in mammalian tissues, and it has the properties of the classic calcium-activated chloride channel (CaCC). This protein has been implicated in numerous major physiological functions. However, the lack of effective and selective blockers has hindered a detailed study of the physiological functions of this channel. In this study, we have developed a potent and selective blocker for endogenous ANO1 in Xenopus laevis oocytes (xANO1) using a drug screening method we previously established (Oh et al., 2008). We have synthesized a number of anthranilic acid derivatives and have determined the correlation between biological activity and the nature and position of substituents in these derived compounds. A structure-activity relationship revealed novel chemical classes of xANO1 blockers. The derivatives contain a-NO2 group on position 5 of a naphthyl group-substituted anthranilic acid, and they fully blocked xANO1 chloride currents with an IC 5050 of 0.08 μM for xANO1. Selectivity tests revealed that other chloride channels such as bestrophin-1, chloride channel protein 2, and cystic fibrosis transmembrane conductance regulator were not appreciably blocked by 10~30 μM MONNA. The potent and selective blockers for ANO1 identified here should permit pharmacological dissection of ANO1/CaCC function and serve as potential candidates for drug therapy of related diseases such as hypertension, cystic fibrosis, bronchitis, asthma, and hyperalgesia.
- Oh, Soo-Jin,Hwang, Seok Jin,Jung, Jonghoon,Yu, Kuai,Kim, Jeongyeon,Choi, Jung Yoon,Hartzell, H. Criss,Roh, Eun Joo,Justin Lee
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supporting information
p. 726 - 735
(2013/11/06)
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- USE OF 9H-PURINE-2,6-DIAMINE DERIVATIVES IN THE TREATMENT OF PROLIFERATIVE DISEASES AND NOVEL 9H-PURINE-2,6-DIAMINE DERIVATIVES
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The invention relates to the use of 9H-purine-2,6-diamine compounds and salts thereof in the treatment of proliferative diseases and for the manufacture of pharmaceutical preparations for the treatment of said diseases, pharmaceutical preparations compris
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Page/Page column 38
(2010/02/14)
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- Benzoindoline compounds
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A compound of formula (I): wherein: R1 and R2 together form a benzo ring optionally substituted by halogen or by alkyl, alkoxy, cyano, nitro, hydroxy, amino, alkylamino, dialkylamino or trifluoromethyl, and R3 and R4
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Page/Page column 4
(2008/06/13)
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- Fluorescent probe for magnesium ion determination
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A fluorescent probe for measuring magnesium ion, which can selectively form a complex with magnesium ion in aqueous system is disclosed. The fluorescent probe for measuring magnesium ion according to the present invention has the structure represented by the following Formula [I]: 1(wherein R1 represents a hydrogen atom, metal atom or an ester-forming group; A represents a group which forms a ring structure together with carbon atom 1 and carbon atom 2; and X is a fluorescent group which may form a condensed ring together with the ring containing the group A).
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- Indoline compounds and to pharmaceutical compositions containing them
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A compound of formula (I): wherein: R1 and R2 together form a benzo ring optionally substituted by halogen or by alkyl, alkoxy, cyano, nitro, hydroxy, amino, alkylamino, dialkylamino or trifluoromethyl, and R3 represents h
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Page/Page column 3-4
(2008/06/13)
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- Palladium-catalyzed synthesis of arylamines from aryl halides and lithium bis(trimethylsilyl)amide as an ammonia equivalent
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(Equation presented) A simple, palladium-catalyzed method to convert aryl halides to the parent anilines using lithium bis(trimethylsilyl)amide (LiN(SiMe3)2) is reported. The reaction is catalyzed by Pd(dba)2 and P(t-Bu)3 and can be run with as little as 0.2 mol % of catalyst. The reaction is faster than competing generation of benzyne intermediates and, therefore, provides the aniline products regiospecifically.
- Lee, Sunwoo,Jorgensen, Morten,Hartwig, John F.
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p. 2729 - 2732
(2007/10/03)
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- Prostaglandin synthase-2 inhibitors
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The present invention provides a compound of the formula: STR1 such compounds are useful for inhibiting prostaglandin synthesis. Pharmaceutical compositions and methods for inhibiting prostaglandin synthesis are also disclosed.
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