- Functionalized π Stacks of Hexabenzoperylenes as a Platform for Chemical and Biological Sensing
-
One challenge in tailoring organic semiconductors for sensing applications is that the introduction of reactive groups or binding sites usually impairs π-π interactions. To meet this challenge, this study puts forth an unusual type of π stacking that allo
- Li, Changqing,Wu, Han,Zhang, Tiankai,Liang, Yujie,Zheng, Bo,Xia, Jiang,Xu, Jianbin,Miao, Qian
-
-
Read Online
- Copper-Catalyzed Conjugate Addition of Carbonyls as Carbanion Equivalent via Hydrazones
-
Copper-catalyzed conjugate addition is a classic method for forming new carbon-carbon bonds. However, copper has never showed catalytic activity for umpolung carbanions in hydrazone chemistry. Herein, we report a facile conjugate addition of hydrazone catalyzed by readily available copper complexes at room temperature. The employment of mesitylcopper(I) and electron-rich phosphine bidentate ligand is a key factor affecting reactivity. The reaction allows various aromatic hydrazones to react with diverse conjugated compounds to produce 1,4-adducts in yields of about 20 to 99%.
- Luo, Siyi,Peng, Marie,Querard, Pierre,Li, Chen-Chen,Li, Chao-Jun
-
p. 13111 - 13117
(2021/09/18)
-
- An Iron-Mesoionic Carbene Complex for Catalytic Intramolecular C-H Amination Utilizing Organic Azides
-
The synthesis of N-heterocycles is of paramount importance for the pharmaceutical industry. They are often synthesized through atom economic and environmentally unfriendly methods, generating significant waste. A less explored, but greener, alternative is
- Albrecht, Martin,Keilwerth, Martin,Meyer, Karsten,Pividori, Daniel M.,Stroek, Wowa
-
supporting information
p. 20157 - 20165
(2021/12/09)
-
- IRIDIUM COMPLEX
-
PROBLEM TO BE SOLVED: To provide iridium which accommodates a wavelength region called a biological window, has a stable excited state, and has an N-hydroxysuccinimide ester group that is a site to bind to a biological substance. SOLUTION: A compound is r
- -
-
Paragraph 0052-0053
(2021/09/01)
-
- SNP discrimination by tolane-modified peptide nucleic acids: Application for the detection of drug resistance in pathogens
-
During the treatment of viral or bacterial infections, it is important to evaluate any resistance to the therapeutic agents used. An amino acid substitution arising from a single base mutation in a particular gene often causes drug resistance in pathogens. Therefore, molecular tools that discriminate a single base mismatch in the target sequence are required for achieving therapeutic success. Here, we synthesized peptide nucleic acids (PNAs) derivatized with tolane via an amide linkage at the N-terminus and succeeded in improving the sequence specificity, even with a mismatched base pair located near the terminal region of the duplex. We assessed the sequence specificities of the tolane-PNAs for single-strand DNA and RNA by UV-melting temperature analysis, thermodynamic analysis, an in silico conformational search, and a gel mobility shift assay. As a result, all of the PNA-tolane derivatives stabilized duplex formation to the matched target sequence without inducing mismatch target binding. Among the different PNA-tolane derivatives, PNA that was modified with a naphthyl-type tolane could efficiently discriminate a mismatched base pair and be utilized for the detection of resistance to neuraminidase inhibitors of the influenza A/H1N1 virus. Therefore, our molecular tool can be used to discriminate single nucleotide polymorphisms that are related to drug resistance in pathogens.
- Ebara, Yasuhito,Hayashi, Tenko,Hori, Sakiko,Kaihatsu, Kunihiro,Kato, Nobuo,Ogata, Katsuya,Okazaki, Miku,Sawada, Shinjiro,Takagi, Kenji
-
supporting information
(2020/02/26)
-
- Rhodium-Catalyzed Remote C(sp3)?H Borylation of Silyl Enol Ethers
-
A rhodium-catalyzed remote C(sp3)?H borylation of silyl enol ethers (SEEs, E/Z mixtures) by alkene isomerization and hydroboration is reported. The reaction exhibits mild reaction conditions and excellent functional-group tolerance. This method is compatible with an array of SEEs, including linear and branched SEEs derived from aldehydes and ketones, and provides direct access to a broad range of structurally diverse 1,n-borylethers in excellent regioselectivities and good yields. These compounds are precursors to various valuable chemicals, such as 1,n-diols and aminoalcohols.
- Li, Jie,Qu, Shuanglin,Zhao, Wanxiang
-
supporting information
p. 2360 - 2364
(2020/01/02)
-
- Efficient C-H Amination Catalysis Using Nickel-Dipyrrin Complexes
-
A dipyrrin-supported nickel catalyst (AdFL)Ni(py) (AdFL: 1,9-di(1-adamantyl)-5-perfluorophenyldipyrrin; py: pyridine) displays productive intramolecular C-H bond amination to afford N-heterocyclic products using aliphatic azide substrates. The catalytic amination conditions are mild, requiring 0.1-2 mol% catalyst loading and operational at room temperature. The scope of C-H bond substrates was explored and benzylic, tertiary, secondary, and primary C-H bonds are successfully aminated. The amination chemoselectivity was examined using substrates featuring multiple activatable C-H bonds. Uniformly, the catalyst showcases high chemoselectivity favoring C-H bonds with lower bond dissociation energy as well as a wide range of functional group tolerance (e.g., ethers, halides, thioetheres, esters, etc.). Sequential cyclization of substrates with ester groups could be achieved, providing facile preparation of an indolizidine framework commonly found in a variety of alkaloids. The amination cyclization reaction mechanism was examined employing nuclear magnetic resonance (NMR) spectroscopy to determine the reaction kinetic profile. A large, primary intermolecular kinetic isotope effect (KIE = 31.9 ± 1.0) suggests H-atom abstraction (HAA) is the rate-determining step, indicative of H-atom tunneling being operative. The reaction rate has first order dependence in the catalyst and zeroth order in substrate, consistent with the resting state of the catalyst as the corresponding nickel iminyl radical. The presence of the nickel iminyl was determined by multinuclear NMR spectroscopy observed during catalysis. The activation parameters (ΔH? = 13.4 ± 0.5 kcal/mol; ΔS?= -24.3 ± 1.7 cal/mol·K) were measured using Eyring analysis, implying a highly ordered transition state during the HAA step. The proposed mechanism of rapid iminyl formation, rate-determining HAA, and subsequent radical recombination was corroborated by intramolecular isotope labeling experiments and theoretical calculations.
- Betley, Theodore A.,Clarke, Ryan M.,Dong, Yuyang,Porter, Gerard J.
-
supporting information
p. 10996 - 11005
(2020/07/08)
-
- PROTEIN KINASE C AGONISTS
-
The present disclosure relates generally to certain diacylglycerol lactone compounds, pharmaceutical compositions comprising said compounds, and methods of making and using said compounds and pharmaceutical compositions. The compounds and compositions disclosed herein may be used for the treatment or prevention of diseases, disorders, or infections modifiable by protein kinase C (PKC) agonists, such as HIV.
- -
-
Paragraph 0339
(2020/09/12)
-
- BIARYL DERIVATIVE AS GPR120 AGONIST
-
The present invention relates to a biaryl derivative expressed by the chemical formula 1, a method for producing the biaryl derivative, a pharmaceutical composition comprising same, and use of same, the biaryl derivative expressed by the chemical formula 1, as a GPR120 agonist, promoting GLP-1 generation in the gastro-intestinal tract, reducing insulin resistance in the liver, muscles and the like from anti-inflammatory activity in the macrophage, pancreatic cells and the like, and allowing effective use in prevention or treatment of inflammation or metabolic diseases such as diabetes, complications from diabetes, obesity, non-alcoholic fatty liver disease, fatty liver disease, and osteoporosis.
- -
-
Paragraph 0149
(2017/11/17)
-
- Metal-Free Enantioselective Oxidative Arylation of Alkenes: Hypervalent-Iodine-Promoted Oxidative C?C Bond Formation
-
The enantioselective oxyarylation of (E)-6-aryl-1-silyloxylhex-3-ene was achieved using a lactate-based chiral hypervalent iodine(III) reagent in the presence of boron trifluoride diethyl etherate. The silyl ether promotes the oxidative cyclization, and enhances the enantioselectivity. In addition, the corresponding aminoarylation was achieved.
- Shimogaki, Mio,Fujita, Morifumi,Sugimura, Takashi
-
supporting information
p. 15797 - 15801
(2016/12/16)
-
- Discovery of a potent and selective free fatty acid receptor 1 agonist with low lipophilicity and high oral bioavailability
-
The free fatty acid receptor 1 (FFA1, also known as GPR40) mediates enhancement of glucose-stimulated insulin secretion and is emerging as a new target for the treatment of type 2 diabetes. Several FFA1 agonists are known, but the majority of these suffer from high lipophilicity. We have previously reported the FFA1 agonist 3 (TUG-424). We here describe the continued structure-activity exploration and optimization of this compound series, leading to the discovery of the more potent agonist 40, a compound with low lipophilicity, excellent in vitro metabolic stability and permeability, complete oral bioavailability, and appreciable efficacy on glucose tolerance in mice.
- Christiansen, Elisabeth,Due-Hansen, Maria E.,Urban, Christian,Grundmann, Manuel,Schmidt, Johannes,Hansen, Steffen V. F.,Hudson, Brian D.,Zaibi, Mohamed,Markussen, Stine B.,Hagesaether, Ellen,Milligan, Graeme,Cawthorne, Michael A.,Kostenis, Evi,Kassack, Matthias U.,Ulven, Trond
-
supporting information
p. 982 - 992
(2013/03/28)
-
- ALKANOIC ACID DERIVATIVES AND THEIR THERAPEUTIC USE AS HDAC INHIBITORS
-
The invention related to alkanoic acid derivatives of Formula (IIa) and (IIb). These compounds of the invention were found to have activity as HDAC inhibitors.
- -
-
Page/Page column 102
(2010/08/05)
-
- CARBOXYLIC DERIVATIVES FOR USE IN THE TREATMENT OF CANCER
-
The invention provides novel compounds of formula (I), wherein: R1 is a radical derived from one of the known ring systems; R2 is a phenyl radical optionally substituted; Xn represents a birradical selected from the group consisting of: -(CH2)1-4-, (C2-C4)-alkenyl, (C2-C4)alkynyl, -S-(CH2)1-3-#, and -(CH2)1-3-O-#; wherein the symbol # indicates the position at which Xn is attached to R1; Yn is a birradical selected from the group consisting of: -(CH2)2-4-, -S-(CH2)1-3#, and -O-(CH2)1-3-#,; where in the symbol # indicates the position at which Yn is attached to R2; and R3 is a radical selected from the group consisting of: -OR4. The compounds of formula (I) are useful in the treatment of cancer
- -
-
Page/Page column 78-79
(2009/07/25)
-
- Retinoid receptor subtype-selective modulators through synthetic modifications of RARγ agonists
-
A series of retinoids designed to interfere with the repositioning of H12 have been synthesized to identify novel RARγ antagonists based on the structure of known RARγ agonists. The transcriptional activities of the novel ligands were revealed by cell-based reporting assays, using engineered cells containg RAR subtype-selective fusions of the RAR ligand-binding domains with the yeast GAL4 activator DNA-binding domain and the cognate luciferase reporter gene. Whereas none of the ligands exhibited features of a selective RARγ antagonist, some of them are endowed with interesting activities. In particular 24a acts as a pan-RAR agonist that induces at high concentration a higher transactivation potential on RARα than TTNPB and synergizes at low concentration with TTNPB-bound RARα but not RARβ or RARγ. Similarly, 24c synergizes with TTNPB-bound RARγ and exhibits RARα,β antagonist activity. Compounds 24b and 25b are strong RARα,β-selective antagonists without agonist or antagonist activities for RARγ. Compounds 24b and 24c display weak RXR antagonist activity. In addition several pan-antagonists and partial agonist/antagonists have been defined.
- Alvarez, Susana,Alvarez, Rosana,Khanwalkar, Harshal,Germain, Pierre,Lemaire, Geraldine,Rodriguez-Barrios, Fatima,Gronemeyer, Hinrich,de Lera, Angel R.
-
supporting information; experimental part
p. 4345 - 4359
(2009/10/17)
-
- Syntheses with organoboranes. XIII. Synthesis of ω-(4-bromophenyl)alkanoic acids and their borylation
-
ω-(4-Bromophenyl)alkanoic acids 2c-e were obtained from 1-bromo-4-alkenylbenzenes 5c-e by hydroboration-thermal isomerization-oxidation. Their esters 11c-e were transformed in good yields into the corresponding boronates 12c-e by the cross-coupling reaction with (10) in an ionic liquid, [bmim][BF4]. The use of pinacolborane for the coupling reaction in the ionic liquid gave debromination products, and low yields of 12c-e. Ethyl 3-(4-bromophenyl)propanoate (7c) was transformed into ethyl 3-(4-[1,3,2]dioxaborolanyl)propanoate (9c) by the cross-coupling with [2,2′]bi[[1,3,2]dioxaborinanyl].
- Zaidlewicz, Marek,Wolan, Andrzej
-
p. 129 - 135
(2007/10/03)
-
- SUBSTITUENT EFFECTS ON THE RATE OF CARBENE FORMATION BY THE PYROLYSIS OF RIGID ARYL SUBSTITUTED DIAZOMETHANES
-
Rate constants for the pyrolysis of 1-diazo-4,4-dimethyl-1,4-dihydronaphtalenes, 4a-4e, have been measured in methanol:6percent triethylamine.In contrast to non-rigid cases, like diphenyldiazomethanes, where all para substituents show a rate increase compared to hydrogen, these rates show a linear Hammett correlation for all para substituents with ?+ = -0.84.This observation is rationalized by a non-linear process for loss of nitrogen leading directly to the ground-state singlet of the carbene, 17.This carbene is then trapped to give ether 11.
- Mathur, Naresh C.,Snow, Miles S.,Young, Kent M.,Pincock, James A.
-
p. 1509 - 1516
(2007/10/02)
-