- Light-Promoted Nickel Catalysis: Etherification of Aryl Electrophiles with Alcohols Catalyzed by a NiII-Aryl Complex
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A highly effective C?O coupling reaction of (hetero)aryl electrophiles with primary and secondary alcohols is reported. Catalyzed by a NiII-aryl complex under long-wave UV (390–395 nm) irradiation in the presence of a soluble amine base without any additional photosensitizer, the reaction enables the etherification of aryl bromides and aryl chlorides as well as sulfonates with a wide range of primary and secondary aliphatic alcohols, affording synthetically important ethers. Intramolecular C?O coupling is also possible. The reaction appears to proceed via a NiI–NiIII catalytic cycle.
- Cao, Rui,Lai, Chu-Hui,Li, Gang,Liu, Fengyi,Lu, Huan-Huan,Wang, Chao,Xiao, Jianliang,Xue, Dong,Yang, Liu,Zhang, Wei
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supporting information
p. 12714 - 12719
(2020/06/02)
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- Synthesis and Structure-Activity Relationships of Triazaspirodecanone Derivatives as Nociceptin/Orphanin FQ Receptor Ligands
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Several spiroxatrine derivatives were synthesized and evaluated as potential NOP receptor ligands. Structural modifications of the 1,4-benzodioxane moiety of spiroxatrine have been the focus of this research project. The structure-activity relationships that emerged indicate that the presence of an H-bond donor group (hydroxyl group) is more favorable for NOP activity when it is positioned α with respect to the CH2 linked to the 1-phenyl-1,3,8-triaza-spiro[4.5]decan-4-one portion. Moreover, cis diastereoisomers of the hydroxyl derivatives4 and 22 show a moderately higher degree of stereoselectivity than trans isomers. In particular, the spiropiperidine derivative cis-4 has submicromolar agonistic activity, and it will be the reference compound for the design and synthesis of new NOP agonists.
- Corrado, Sandra,Battisti, Umberto M.,Sorbi, Claudia,Tait, Annalisa,Malfacini, Davide,Camarda, Valeria,Calò, Girolamo,Brasili, Livio
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p. 447 - 458
(2015/02/19)
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- Systematic methodology for the development of biocatalytic hydrogen-borrowing cascades: Application to the synthesis of chiral α-substituted carboxylic acids from α-substituted α,β-unsaturated aldehydes
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Ene-reductases (ERs) are flavin dependent enzymes that catalyze the asymmetric reduction of activated carbon-carbon double bonds. In particular, α,β-unsaturated carbonyl compounds (e.g. enals and enones) as well as nitroalkenes are rapidly reduced. Conversely, α,β-unsaturated esters are poorly accepted substrates whereas free carboxylic acids are not converted at all. The only exceptions are α,β-unsaturated diacids, diesters as well as esters bearing an electron-withdrawing group in α- or β-position. Here, we present an alternative approach that has a general applicability for directly obtaining diverse chiral α-substituted carboxylic acids. This approach combines two enzyme classes, namely ERs and aldehyde dehydrogenases (Ald-DHs), in a concurrent reductive-oxidative biocatalytic cascade. This strategy has several advantages as the starting material is an α-substituted α,β-unsaturated aldehyde, a class of compounds extremely reactive for the reduction of the alkene moiety. Furthermore no external hydride source from a sacrificial substrate (e.g. glucose, formate) is required since the hydride for the first reductive step is liberated in the second oxidative step. Such a process is defined as a hydrogen-borrowing cascade. This methodology has wide applicability as it was successfully applied to the synthesis of chiral substituted hydrocinnamic acids, aliphatic acids, heterocycles and even acetylated amino acids with elevated yield, chemo- and stereo-selectivity. A systematic methodology for optimizing the hydrogen-borrowing two-enzyme synthesis of α-chiral substituted carboxylic acids was developed. This systematic methodology has general applicability for the development of diverse hydrogen-borrowing processes that possess the highest atom efficiency and the lowest environmental impact. This journal is
- Knaus, Tanja,Mutti, Francesco G.,Humphreys, Luke D.,Turner, Nicholas J.,Scrutton, Nigel S.
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supporting information
p. 223 - 233
(2015/02/19)
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- Synthesis of robalzotan, ebalzotan, and rotigotine precursors via the stereoselective multienzymatic cascade reduction of α,β-unsaturated aldehydes
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A stereoselective synthesis of bicyclic primary or secondary amines, based on tetralin or chroman structural moieties, is reported. These amines are precursors of important active pharmaceutical ingredients such as rotigotine (Neupro), robalzotan, and eba
- Brenna, Elisabetta,Gatti, Francesco G.,Malpezzi, Luciana,Monti, Daniela,Parmeggiani, Fabio,Sacchetti, Alessandro
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p. 4811 - 4822
(2013/07/05)
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- Compounds that modulate PPAR activity and methods of preparation
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This invention discloses compounds that alter PPAR activity. The invention also discloses pharmaceutically acceptable salts of the compounds, pharmaceutically acceptable compositions comprising the compounds or their salts, and methods of using them as therapeutic agents for treating or preventing hyperlipidemia and hypercholesteremia in a mammal. The present invention also discloses method for making the disclosed compounds.
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- Pharmacomodulation d'adrenolytiques α en serie benzopyrannique
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Pharmacomodulation of α-adrenergic blocking agents by a series of benzopyrans.The N-methylpiperidine fragment was associated with four oxygenated heterocycles of the benzopyran ring system.Two different synthesis pathways were used in each case.Twenty intermediate derivatives and four aminomethylated derivatives whose structures were established by spectroscopic data are described.The pharmacological investigation demonstrates the interest of these compounds on the α-adrenergic receptors in light of their activities and selectivities. α1-adrenergic blocking agents / α2-adrenergic blocking agents / piperidinomethyl chromone, chromene and chromane
- Mouysset, Genevieve,Payard, Marc,Grassy, Gerard,Tronche, Pierre,Dabire, Hubert,et al.
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p. 539 - 544
(2007/10/02)
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- Reactions of Co-ordinated Ligands. Part 10. Rhodium-catalysed Cyclisation of 3-(2-Fluorophenyl)propanols to Chromans
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The cyclisation of several 3-(2-fluorophenyl)-propanols to the corresponding chroman occurs in nitromethane-acetone solution at 80 deg C when either the hexafluorophosphate (3) or tetrafluoroborate salt (4) of the (η5-ethyltetramethylcyclopentadienyl)(η6-benzene)rhodium(III) cation is used as a catalyst; the former salt is the more effective catalyst.The cyclisation is believed to involve the activation of the aryl fluoride (towards intramolecular nucleophilic substitution by the hydroxy group) by the formation of a metal complex in which the aryl fluoride is ?-bonded with the metal cation.It is suggested that the arene-exchange reaction which gives this ?-bonded complex proceeds faster with the salt (3) than with the salt (4), and that this is the main factor for the greater efficiency of the former salt as a cyclisation catalyst.
- Houghton, Roy P.,Voyle, Martyn,Price, Raymond
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p. 925 - 931
(2007/10/02)
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- Intramolecular Nucleophilic Substitutions of Co-ordinated Aryl Halides. A Preparation of Chromans
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3-(o-Fluorophenyl)propan-1-ol can be cyclised readily to chroman either through chromium tricarbonyl complexes or (as also with substituted fluorophenylpropanols) by the action of the (η6-benzene)(η5-ethyltetramethylcyclopentadienyl)
- Houghton, Roy P.,Voyle, Martyn,Price, Raymond
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p. 884 - 885
(2007/10/02)
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