- Gold(I)-Catalyzed Reactivity of Furan-ynes with N-Oxides: Synthesis of Substituted Dihydropyridinones and Pyranones
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The reactivity of "furan-ynes"in combination with pyridine and quinoline N-oxides in the presence of a Au(I) catalyst, has been studied, enabling the synthesis of three different heterocyclic scaffolds. Selective access to two out of the three possible products, a dihydropyridinone and a furan enone, has been achieved through the fine-tuning of the reaction conditions. The reactions proceed smoothly at room temperature and open-air, and were further extended to a broad substrate scope, thus affording functionalized dihydropyridinones and pyranones.
- Maranzana, Andrea,Marra, Francesco,Nejrotti, Stefano,Prandi, Cristina,Priola, Emanuele
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supporting information
p. 8295 - 8307
(2021/07/02)
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- Design and synthesis of furyl/thineyl pyrroloquinolones based on natural alkaloid perlolyrine, lead to the discovery of potent and selective PDE5 inhibitors
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Based on perlolyrine (1), a natural alkaloid with weak PDE5 potency from the traditional Chinese aphrodisiac plant Tribulus terrestris L., a series α-substituted tetrahydro-β-carboline (THβC) derivatives were synthesized via T+BF4--mediated oxidative C–H functionalization of N-aryl THβCs with diverse potassium trifluoroborates. Following Winterfeldt oxidation afforded the corresponding furyl/thienyl pyrroloquinolones, of which 5-ethylthiophene/ethylfuran derivatives 20a–b were identified as the most potent and selective PDE5 inhibitors. Among the enantiomers, (S)-20a and (S)-20b (IC50 = 0.52 and 0.39 nM) were found to be more effective than their (R)-antipode, display favorable pharmacokinetic profiles, exert in vitro vasorelaxant effects on the isolated thoracic aorta, and exhibit in vivo efficacy in the anesthetized rabbit erectile model.
- Zheng, Hongbo,Li, Lin,Sun, Bin,Gao, Yun,Song, Wei,Zhao, Xiaoyu,Gao, Yanhui,Xie, Zhiyu,Zhang, Nianzhao,Ji, Jianbo,Yuan, Huiqing,Lou, Hongxiang
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supporting information
p. 30 - 38
(2018/03/08)
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- METALLOCENE COMPLEX AND OLEFIN POLYMERIZATION METHOD
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Provided are a metallocene complex that facilitates copolymerization of olefin monomers including propylene at a higher uptake rate of comonomers, i.e., ethylene and α-olefin, manufacture of a rubber component having a higher molecular weight, and manufac
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Paragraph 0147; 0260
(2015/11/03)
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- Organotrifluoroborate hydrolysis: Boronic acid release mechanism and an acid-base paradox in cross-coupling
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The hydrolysis of potassium organotrifluoroborate (RBF3K) reagents to the corresponding boronic acids (RB(OH)2) has been studied in the context of their application in Suzuki-Miyaura coupling. The "slow release" strategy in such SM couplings is only viable if there is an appropriate gearing of the hydrolysis rate of the RBF3K reagent with the rate of catalytic turnover. In such cases, the boronic acid RB(OH)2 does not substantially accumulate, thereby minimizing side reactions such as oxidative homocoupling and protodeboronation. The study reveals that the hydrolysis rates (THF, H2O, Cs2CO 3, 55 °C) depend on a number of variables, resulting in complex solvolytic profiles with some RBF3K reagents. For example, those based on p-F-phenyl, naphthyl, furyl, and benzyl moieties are found to require acid catalysis for efficient hydrolysis. This acid-base paradox assures their slow hydrolysis under basic Suzuki-Miyaura coupling conditions. However, partial phase-splitting of the THF/H2O induced by the Cs2CO 3, resulting in a lower pH in the bulk medium, causes the reaction vessel shape, material, size, and stirring rate to have a profound impact on the hydrolysis profile. In contrast, reagents bearing, for example, isopropyl, β-styryl, and anisyl moieties undergo efficient "direct" hydrolysis, resulting in fast release of the boronic acid while reagents bearing, for example, alkynyl or nitrophenyl moieties, hydrolyze extremely slowly. Analysis of B-F bond lengths (DFT) in the intermediate difluoroborane, or the Swain-Lupton resonance parameter (R) of the R group in RBF3K, allows an a priori evaluation of whether an RBF3K reagent will likely engender "fast", "slow", or "very slow" hydrolysis. An exception to this correlation was found with vinyl-BF 3K, this reagent being sufficiently hydrophilic to partition substantially into the predominantly aqueous minor biphase, where it is rapidly hydrolyzed.
- Lennox, Alastair J. J.,Lloyd-Jones, Guy C.
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p. 7431 - 7441
(2012/06/16)
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- SLOW RELEASE OF ORGANOBORONIC ACIDS IN CROSS-COUPLING REACTIONS
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A method of performing a chemical reaction includes reacting a compound selected from the group consisting of an organohalide and an organo-pseudohalide, and a protected organoboronic acid represented by formula (I) in a reaction mixture: R1-B-T; where R1 represents an organic group, T represents a conformationalIy rigid protecting group, and B represents boron having sp3 hybridization. When unprotected, the corresponding organoboronic acid is unstable by the boronic acid neat stability test. The reaction mixture further includes a base having a pKB of at least 1 and a pal ladium catalyst. The method further includes forming a cross-coupled product in the reaction mixture.
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Page/Page column 41
(2010/04/27)
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- Solvent applications of 2-methyltetrahydrofuran in organometallic and biphasic reactions
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2-Methyltetrahydrofuran (MeTHF) is a commercially available solvent that is produced from renewable resources. The properties of MeTHF place it between tetrahydrofuran (THF) and diethyl ether in solvent polarity and Lewis base strength. In many cases, MeTHF can replace THF in organometallic reactions. The formation and reaction of Grignard reagents in MeTHF and THF are similar. MeTHF can be used as a solvent for low-temperature lithiation, for lithium aluminum hydride reductions, for the Reformatsky reaction, and for metal-catalyzed coupling reactions. MeTHF is also a good substitute for dichloromethane in biphasic reactions.
- Aycock, David F.
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p. 156 - 159
(2012/12/26)
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- COMPOUNDS, COMPOSITIONS AND METHODS
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The present invention provides methods and pharmaceutical compositions for inhibiting expressions of HIF and HIF regulated genes, inhibiting angiogenesis, inducing cell cycle arrest in tumor cells, and treating cell proliferating diseases or conditions.
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- METHOD FOR METAL-ORGANIC PRODUCTION OF ORGANIC INTERMEDIATE PRODUCTS BY MEANS OF ARYL LITHIUM-BASES
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The invention relates to a method for the production of substituted aromatic compounds by producing lithium arylene and by reacting it with suitable electrophiles. The method comprises the following steps (step 1); an aryl lithium compound ( auxiliary base'') is initially produced by reacting a halogen aromatic compound with lithium metal; said compound is subsequently (step 2) reacted for deprotonation of the aromatic substrate in order to form the corresponding lithium aromatic compound which is subsequently (step 3) reacted with a corresponding electrophile to form the desired substituted aromatic compound, see page 2 of the description.
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Page/Page column 15-16
(2010/02/06)
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- Process for preparing boronic and borinic acids
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A process for preparing boronic acids of the formula (I) and borinic acids of the formula (II), by reaction of chloroaromatics of the formula (III) with lithium metal and boron compounds BW′W′W′″, where W′, W′ and W′″ are each, independently of one another, C1-C6-alkoxy, fluorine, chlorine, bromine, iodine, N(C1-C6-alkyl)2 or S(C1-C5-alkyl), in a solvent at temperatures in the range from ?100 to 80° C.
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- Urokinase inhibitors
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Compounds having the formula are inhibitors of urokinase and are useful in the treatment of diseases in which urokinase plays a role. Also disclosed are urokinase-inhibiting compositions and a method of inhibiting urokinase in a mammal.
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- Ukokinase inhibitors
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Compounds having the formula are inhibitors of urokinase and are useful in the treatment of diseases in which urokinase plays a role. Also disclosed are urokinase-inhibiting compositions and a method of inhibiting urokinase in a mammal.
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- Polyheterocyclic compounds
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The present invention relates to a group of polyheterocyclic compounds covered by the following formula: STR1 wherein each of X1, X2, X3, and X4, independently, is O, S, NH, or N(C1-6 alkyl), but one of them must be O, NH, or N(C1-6 alkyl); each of R1, R2, R5, and R6, independently, is H or a substituent (e.g., halogen, CN, NO2, or C1-4 haloalkyl), but at least one of them must be a substituent; each of R3 and R4, independently, is H, C1-6 alkyl, CHO, CH2 OH, or CH2 NH2 ; and each of m and n, independently, is 0 or 1.
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- ISOPRENYL TRANSFERASE INHIBITORS
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Peptidomimetic compounds useful in the treatment of Ras-associated human cancers, and other conditions mediated by farnesylated or geranylgeranylated proteins; and synthetic intermediates thereof
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