- Reduction of Electron-Deficient Alkenes Enabled by a Photoinduced Hydrogen Atom Transfer
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Direct hydrogen atom transfer from a photoredox-generated Hantzsch ester radical cation to electron-deficient alkenes has enabled the development of an efficient formal hydrogenation under mild, operationally simple conditions. The HAT-driven mechanism is supported by experimental and computational studies. The reaction is applied to a variety of cinnamate derivatives and related structures, irrespective of the presence of electron-donating or electron-withdrawing substituents in the aromatic ring and with good functional group compatibility. (Figure presented.).
- Larionova, Natalia A.,Ondozabal, Jun Miyatake,Cambeiro, Xacobe C.
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p. 558 - 564
(2020/12/07)
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- Remote Functionalization of α,β-Unsaturated Carbonyls by Multimetallic Sequential Catalysis
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The remote functionalization of α,β-unsaturated carbonyls by an array of multimetallic sequential catalytic systems is described. The reactions are triggered by hydrometalation using [Pd-H] or [Ru-H] isomerization catalysts and driven by the formation of thermodynamically more stable 1,2-vinyl arenes. The Pd-catalyzed deconjugative isomerization was combined with a Cu-catalyzed β-borylation of the transiently generated styrenyl derivatives to deliver a range of products that would not be accessible with the use of a single catalyst. [Pd/Cu] catalytic systems were also identified for the highly enantioselective α-hydroboration and α-hydroamination of the styrenyl intermediates. Difunctionalization simultaneously at the benzylic and homobenzylic positions was achieved by combining the isomerization process with Sharpless asymmetric dihydroxylation (SAD) using [Pd/Os] or [Ru/Os] couples. Starting from a simple α,β-unsaturated ester, an isomerization/dihydroxylation/lactonization sequence gave access to a naturally occurring γ-butyrolactone in good yield, with excellent diastereo- and enantioselectivity.
- Romano, Ciro,Fiorito, Daniele,Mazet, Clément
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supporting information
p. 16983 - 16990
(2019/10/28)
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- Conformationally rigid derivatives of WAY-267,464: Synthesis and pharmacology at the human oxytocin and vasopressin-1a receptors
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WAY-267,464 (1) and twelve conformationally rigid analogues (3a-f–4a-f) were synthesised, characterised and evaluated in cellular assays with the aim of systematically exploring interactions with the oxytocin receptor (OTR). Each analogue was evaluated in
- Jorgensen, William T.,Gulliver, Damien W.,Katte, Timothy A.,Werry, Eryn L.,Reekie, Tristan A.,Connor, Mark,Kassiou, Michael
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p. 1644 - 1656
(2017/11/13)
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- Synthesis of N-Substituted Condensed Tetrahydropyridine-Based Enaminones via Palladium-Catalyzed Intramolecular C–N Cross-coupling
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A number of β-enaminones with secondary amino group (alkyl, cyclopropyl, and aryl) were prepared from corresponding β-diketones. Two general protocols for their palladium-catalyzed intramolecular C–N cross-coupling were established to give corresponding N-substituted condensed tetrahydropyridines in good yields. The methodology is applicable for a wide variety of structural motifs. The work also extends the applicability of novel, recently established, palladium precatalysts to new substrates.
- Dou?ová, Hana,R??i?ková, Zdeňka,?im?nek, Petr
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p. 670 - 684
(2018/01/22)
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- 1,3,8-TRIAZASPIRO[4,5]DECAN-4-ONE DERIVATIVES USEFUL FOR THE TREATMENT OF ORL-1 RECEPTOR MEDIATED DISORDERS
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The present invention is directed to novel 1,3,8-triazaspiro[4.5]decan-4-one derivatives of the general formulawherein all variables are as defined herein, useful in the treatment of disorders and conditions mediated by the ORL-1 G-protein coupled receptor. More particularly, the compounds of the present invention are useful in the treatment of disorders and conditions such as anxiety, depression, substance abuse, neuropathic pain, acute pain, migraine, asthma, cough and for improved cognition.
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Paragraph 0225-0227
(2017/02/28)
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- Metal-Free Enantioselective Oxidative Arylation of Alkenes: Hypervalent-Iodine-Promoted Oxidative C?C Bond Formation
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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
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supporting information
p. 15797 - 15801
(2016/12/16)
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- An intramolecular C-N cross-coupling of β-enaminones: A simple and efficient way to precursors of some alkaloids of Galipea officinalis
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2-Aroylmethylidene-1,2,3,4-tetrahydroquinolines with the appropriate substituents can be suitable precursors for the synthesis of alkaloids from Galipea officinalis (cuspareine, galipeine, galipinine, angustureine). However, only two, rather low-yielding procedures for their synthesis are described in the literature. We have developed a simple and efficient protocol for an intramolecular, palladium or copper-catalysed amination of both chloro- and bromo-substituted 3-amino-1,5-diphenylpent-2-en-1-ones leading to the above-mentioned tetrahydroquinoline moiety. The methodology is superior to the methods published to date.
- Douov, Hana,Hork, Radim,Ruikov, Zdeka,imunek, Petr
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p. 884 - 892
(2015/08/24)
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- Bimolecular coupling reactions through oxidatively generated aromatic cations: Scope and stereocontrol
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Chromenes, isochromenes, and benzoxathioles react with 2,3-dichloro-5,6- dicyano-1,4-benzoquinone to form stable aromatic cations that react with a range of nucleophiles. These oxidative fragment coupling reactions provide rapid access to structurally div
- Cui, Yubo,Villafane, Louis A.,Clausen, Dane J.,Floreancig, Paul E.
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p. 7618 - 7626
(2013/08/23)
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- Copper-catalyzed cross-coupling of O -alkyl hydroxamates with aryl iodides
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N-Aryl-O-alkylhydroxamic acid derivatives were prepared by copper-catalyzed cross-coupling of hydroxamates with aryl iodides. The reaction conditions are compatible with standard hydroxy-protecting groups on the hydroxylamine moiety and are applicable to
- Kukosha, Tatyana,Trufilkina, Nadezhda,Belyakov, Sergey,Katkevics, Martins
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supporting information; experimental part
p. 2413 - 2423
(2012/09/07)
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- Identification of a new biaryl scaffold generating potent renin inhibitors
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The discovery and SAR of a series of potent renin inhibitors possessing a novel biaryl scaffold are described herein. Molecular modeling revealed that the cyclopropylamide spacer present in 1 can be replaced by a simple, substituted aromatic ring such as
- Lacombe, Patrick,Aspiotis, Renée,Bayly, Christopher,Chen, Austin,Dubé, Daniel,Fortin, Réjean,Gallant, Michel,Juteau, Hélne,Liu, Suzanna,McKay, Dan,Roy, Patrick,Wu, Tom
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scheme or table
p. 5822 - 5826
(2010/12/19)
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- Development of a bio-inspired acyl-anion equivalent macrocyclization and synthesis of a trans-resorcylide precursor
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(Chemical Equation Presented) Studies on the macrocyclization of α,ω-dialdehydes have revealed a strong dependence on ring size with respect to the ultimate efficiency of the reaction. Strong catalyst dependence was observed, as thiazolium salts led to no detectable product formation, whereas electron-deficient triazolium salts served as precatalysts for the cyclization. Surprisingly, the N-pentafluorophenyl triazolium variant led to cyclization at room temperature within a short 90-min reaction time. These findings were applied to a range of substrates, including the synthesis of a key intermediate in a rapid synthesis of trans-resorcylide.
- Mennen, Steven M.,Miller, Scott J.
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p. 5260 - 5269
(2008/02/07)
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- Highly regioselective anti-markovnikov palladium-borate-catalyzed methoxycarbonylation reactions: Unprecedented results for aryl olefins
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(Chemical Equation Presented) A general, highly efficient and regioselective methoxycarbonylation, by means of a palladium-salicylicborate- catalyzed protocol, of terminal alkyl and aryl olefins is described. The substrates include aliphatic alkenes, allylbenzenes, and styrene derivatives. The yields are very good (60-92%) and the regioselectivity, in favor of the linear ester, is up to quantitative - unprecedented in the case of styrenes.
- Vieira, Tiago O.,Green, Mike J.,Alper, Howard
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p. 6143 - 6145
(2007/10/03)
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- 1,3,8-Triazaspiro[4.5]decan-4-one derivatives useful for the treatment of ORL-1 receptor mediated disorders
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The present invention is directed to novel 1,3,8-triazaspiro[4.5]decan-4-one derivatives of the general formula wherein all variables are as defined herein, useful in the treatment of disorders and conditions mediated by the ORL-1 G-protein coupled receptor. More particularly, the compounds of the present invention are useful in the treatment of disorders and conditions such as anxiety, depression, substance abuse, neuropathic pain, acute pain, migraine, asthma, cough and for improved cognition.
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- Interphenylene 7-oxabicyclo[2.2.1]heptane thromboxane A2 antagonists. Semicarbazone ω-chains
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A series of chiral interphenylene 7-oxabicyclo[2.2.1]heptane semicarbazones 19-26 were prepared and evaluated for their in vitro thromboxane (TxA2) antagonistic activity and in vivo duration of action. The potency of 19-26 was found to be highly dependent on the substitution pattern of the interphenylene ring and decreased in the order ortho > meta >> para. SQ 35,091 (25), [1S-(1α,2α,3α,4α)]-2-[[3-[[[(phenylamino)carbonyl]hydrazono] methyl]-7-oxabicyclo[2.2.1]hept-2-yl]methyl]benzenepropanoic acid, was identified as a potent and long-acting TxA2 antagonist. In human platelet rich plasma SQ 35,091 inhibited arachidonic acid (800 μM) and U-46,619 (10 μM) induced aggregation with I50 values of 3 and 12 nM, respectively. In contrast, no inhibition of ADP (20 μM) induced aggregation was observed at >1000 μM. Receptor binding studies with [3H]-SQ 29,548 showed SQ 35,091 was a competitive antagonist with a K(d) value of 1.0 ± 0.1 nM in human platelet membranes. In vivo SQ 35,091 (0.2 mg/kg po) showed extended protection (T50 = 16 h) from U-46,619 (2 mg/kg iv) induced death in mice. These compounds have for the first time demonstrated that a metabolically stable interphenylene α-sidechain can be introduced into a prostanoid-like series of TxA2 antagonists with the maintenance of potent antagonistic activity.
- Misra,Brown,Han,Harris,Hedberg,Webb,Hall
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p. 2882 - 2891
(2007/10/02)
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- Palladium catalyzed synthesis of annelated indoles
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The synthesis of polycyclic indoles is shown to be accomplished readily by the palladium catalyzed intramolecular cyclization of bromoaryl bearing indoles.
- Kozikowski,Ma
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p. 3317 - 3320
(2007/10/02)
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- Novel compounds
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A compound of formula (I): STR1 or a salt, ester or amide thereof, in which Y is a group --O(CH2)m --, --(CH2)m -- or --CH=CH-- where m is an integer of from 1 to 5 n is an integer of from 4 to 14 X represents a double or triple bond, and each of A and B represents hydrogen when X is a double bond, or both A and B are absent when X is a triple bond, is useful in the treatment of allergic diseases.
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