- Selective hydrogenation of α,β-unsaturated carbonyl compounds on silica-supported copper nanoparticles
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Silica-supported copper nanoparticles prepared via surface organometallic chemistry are highly efficient for the selective hydrogenation of various α,β-unsaturated carbonyl compounds yielding the corresponding saturated esters, ketones, and aldehydes in the absence of additives. High conversions and selectivities (>99%) are obtained for most substrates upon hydrogenation at 100-150 °C and under 25 bar of H2.
- Mendes-Burak, Jorge,Ghaffari, Behnaz,Copéret, Christophe
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supporting information
p. 179 - 181
(2019/01/04)
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- Improving the Potency of Cancer Immunotherapy by Dual Targeting of IDO1 and DNA
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Herein we report the first exploration of a dual-targeting drug design strategy to improve the efficacy of small-molecule cancer immunotherapy. New hybrids of indoleamine 2,3-dioxygenase 1 (IDO1) inhibitors and DNA alkylating nitrogen mustards that respectively target IDO1 and DNA were rationally designed. As the first-in-class examples of such molecules, they were found to exhibit significantly enhanced anticancer activity in vitro and in vivo with low toxicity. This proof-of-concept study has established a critical step toward the development of a novel and effective immunotherapy for the treatment of cancers.
- Fang, Kun,Dong, Guoqiang,Wang, Hongyu,He, Shipeng,Wu, Shanchao,Wang, Wei,Sheng, Chunquan
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supporting information
p. 30 - 36
(2017/12/26)
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- Preparation method of triazole compound
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The invention discloses a preparation method of a triazole compound, namely N-((5-(4-nitrophenyl)-2H-1,2,4-triazole-3-yl)methyl)-N-propyl-1-propylamine. The preparation method takes 3-(4-nitrophenyl) ethyl acrylate as a starting material and a target prod
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Paragraph 0025; 0026
(2017/08/30)
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- 4-alkyloxyimino derivatives of uridine-5′-triphosphate: Distal modification of potent agonists as a strategy for molecular probes of P2Y 2, P2Y4, and P2Y6 receptors
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Extended N4-(3-arylpropyl)oxy derivatives of uridine-5′-triphosphate were synthesized and potently stimulated phospholipase C stimulation in astrocytoma cells expressing G protein-coupled human (h) P2Y receptors (P2YRs) activated by UTP (P2Y2/4R) or UDP (P2Y6R). The potent P2Y4R-selective N4-(3- phenylpropyl)oxy agonist was phenyl ring-substituted or replaced with terminal heterocyclic or naphthyl rings with retention of P2YR potency. This broad tolerance for steric bulk in a distal region was not observed for dinucleoside tetraphosphate agonists with both nucleobases substituted. The potent N 4-(3-(4-methoxyphenyl)-propyl)oxy analogue 19 (EC50: P2Y2R, 47 nM; P2Y4R, 23 nM) was functionalized for chain extension using click tethering of fluorophores as prosthetic groups. The BODIPY 630/650 conjugate 28 (MRS4162) exhibited EC50 values of 70, 66, and 23 nM at the hP2Y2/4/6Rs, respectively, and specifically labeled cells expressing the P2Y6R. Thus, an extended N4-(3- arylpropyl)oxy group accessed a structurally permissive region on three G q-coupled P2YRs, and potency and selectivity were modulated by distal structural changes. This freedom of substitution was utilized to design of a pan-agonist fluorescent probe of a subset of uracil nucleotide-activated hP2YRs.
- Jayasekara, P. Suresh,Barrett, Matthew O.,Ball, Christopher B.,Brown, Kyle A.,Hammes, Eva,Balasubramanian, Ramachandran,Harden, T. Kendall,Jacobson, Kenneth A.
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p. 3874 - 3883
(2014/05/20)
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- Reduction of alkenes catalyzed by copper nanoparticles supported on diamond nanoparticles
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Copper nanoparticles (Cu NPs) supported on diamond nanoparticles (D NPs) previously purified by Fenton treatment (Cu/D) followed by annealing with hydrogen (Cu/DH) are highly efficient and reusable heterogeneous catalysts for hydrogenation of styrene to ethylbenzene with the minimum productivity value of 30617 cycles. The Royal Society of Chemistry.
- Dhakshinamoorthy, Amarajothi,Navalon, Sergio,Sempere, David,Alvaro, Mercedes,Garcia, Hermenegildo
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supporting information
p. 2359 - 2361
(2013/07/05)
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- Fluorous oxime palladacycle: A precatalyst for carbon-carbon coupling reactions in aqueous and organic medium
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To facilitate precatalyst recovery and reuse, we have developed a fluorous, oxime-based palladacycle 1 and demonstrated that it is a very efficient and versatile precatalyst for a wide range of carbon-carbon bond formation reactions (Suzuki-Miyaura, Sonogashira, Stille, Heck, Glaser-type, and Kumada) in either aqueous or organic medium under microwave irradiation. Palladacycle 1 could be recovered through F-SPE in various coupling reactions with recovery ranging from 84 to 95% for the first cycle. Inductively coupled plasma optical emission spectrometry (ICP-OES) analyses of the Pd content in the crude product from each class of transformation indicated extremely low levels of leaching and the palladacycle could be reused four to five times without significant loss of activity.
- Susanto, Woen,Chu, Chi-Yuan,Ang, Wei Jie,Chou, Tzyy-Chao,Lo, Lee-Chiang,Lam, Yulin
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experimental part
p. 2729 - 2742
(2012/05/21)
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- Highly active iridium(i) complexes for the selective hydrogenation of carbon-carbon multiple bonds
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New iridium(i) complexes, bearing a bulky NHC/phosphine ligand combination, have been established as extremely efficient hydrogenation catalysts that can be used at low catalyst loadings, and are compatible with functional groups which are often sensitive to more routinely employed hydrogenation methods.
- Bennie, Linsey S.,Fraser, Calum J.,Irvine, Stephanie,Kerr, William J.,Andersson, Shalini,Nilsson, Goeran N.
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supporting information; experimental part
p. 11653 - 11655
(2011/12/05)
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- Tandem β-boration/arylation of α,β-unsaturated carbonyl compounds by using a single palladium complex to catalyse both steps
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Diphenyl(3-methyl-2-indolyl)phosphine (C9H8NPPh 2, 1) gives stable dimeric palladium(II) complexes that contain the phosphine in P,Nbridging coordination mode. On treating 1 with [Pd(O 2CCH3)2], the new complexes [Pd(μ-C 9H7NPPh2)-(NCCH3)]2 (2) or [Pd(μ-C9H7NPPh2)-(μ-O 2CCH3)]2 (3) were isolated, depending on the solvent used, acetonitrile or toluene, respectively. Further reaction of 3 with the ammonium salt of 1 led to the substitution of one carboxylate ligand to afford [Pd(u-C9H7NPPh2)3(μ-O 2CCH3)] (4), in which the bimetallic unit is bonded by three C9H7NPPh2- moieties and one carboxylate group. Using this methodology, [Pd2(μ-C 6H4PPh2)2(μ-C9H 7NPPh2)(μ-O2CCX3)] (X = H (7); J. = F (8)) were synthesised from the ortho-metalated compounds [Pd(C 6H4PPh2)(μO2CCX3)], (X = H (5); J. = F (6)). Complexes 3, 4, 7, and 8 have been found to be active in the catalytic β-boration of α,β-unsaturated esters and ketones under mild reaction conditions. Hindrance of the carbonyl moiety has an influence on the reaction rate, but quantitative conversion was achieved in many cases. More remarkably, when aryl bromides were added to the reaction media, complex 7 induced a highly successful consecutive β-boration/crosscoupling reaction with dimethyl acrylamide as the substrate (99% conversion, 89 % isolated yield).
- Bonet, Amadeu,Gulyas, Henrik,Koshevoy, Igor O.,Estevan, Francisco,Sanau, Mercedes,Ubeda, M. Angeles,Fernandez, Elena
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supporting information; experimental part
p. 6382 - 6390
(2010/08/03)
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- Original TDAE strategy using α-halocarbonyl derivatives
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We report herein the selective C-C bond formation by the reaction of nitrobenzyl carbanions, formed via the TDAE strategy, with α-haloesters and α-haloamides. This reaction, extended in benzodioxole and dimethoxybenzene series provides new potentially CNS
- Since, Marc,Terme, Thierry,Vanelle, Patrice
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experimental part
p. 6128 - 6134
(2011/03/19)
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- Acrolein diethyl acetal: A three-carbon homologating reagent for the synthesis of β-arylpropanoates and cinnamaldehydes by heck reaction catalyzed by a Kaiser oxime resin derived palladacycle
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A polymer palladacycle derived from Kaiser oxime resin was used as a source of palladium(0) in the chemoselective Heck reaction of acrolein diethyl acetal with aryl halides under ligand-free conditions. The use of typical Heck conditions afforded 3-arylpropionic esters, and the process can be directed to the synthesis of cinnamaldehydes under Cacchi conditions. These processes take place with rather low loading of the catalyst, which can be recovered by simple filtration and reused for at least five runs without competitive dehalogenation. This is the first time that a supported palladium complex has been reused under Cacchi conditions. ICP-OES analyses of the Pd content of the crude products in both transformations indicated lower leaching for the esters than for the aldehydes in the range up to 0.08 ppm for the esters and 0.8 ppm for the aldehydes. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Alacid, Emilio,Najera, Carmen
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experimental part
p. 3102 - 3106
(2009/04/11)
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- Structure-activity relationships of phenylpropanoids as antifeedants for the pine weevil Hylobius abietis
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Ethyl cinnamate has been isolated from the bark of Pinus contorta in the search for antifeedants for the pine weevil, Hylobius abietis. Based on this lead compound, a number of structurally related compounds were synthesized and tested. The usability of the Topliss scheme, a flow diagram previously used in numerous structure-activity relationship (SAR) studies, was evaluated in an attempt to find the most potent antifeedants. The scheme was initially followed stepwise; subsequently, all compounds found in the scheme were compared. In total, 51 phenylpropanoids were tested and analyzed for SARs by using arguments from the field of medicinal chemistry (rational drug design). Individual Hansch parameters based on hydrophobicity, steric, and electronic properties were examined. The effects of position and numbers of substituents on the aromatic ring, the effects of conjugation in the molecules, and the effects of the properties of the parent alcohol part of the esters were also evaluated. It proved difficult to find strong SARs derived from single physicochemical descriptors, but our study led to numerous new, potent, phenylpropanoid antifeedants for the pine weevil. Among the most potent were methyl 3-phenylpropanoates monosubstituted with chloro, fluoro, or methyl groups and the 3,4-dichlorinated methyl 3-phenylpropanoate.
- Bohman,Nordlander,Nordenhem,Sunnerheim,Borg-Karlson,Unelius
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p. 339 - 352
(2008/09/18)
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- Chemoselective Heck arylation of acrolein diethyl acetal catalyzed by an oxime-derived palladacycle
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A dimeric 4-hydroxyacetophenone oxime-derived palladacycle has been used as a very efficient precatalyst for the chemoselective arylation of acrolein diethyl acetal to give either cinnamaldehyde derivatives or 3-arylpropanoate esters by proper choice of the reaction conditions. The synthesis of cinnamaldehyde derivatives can be performed by Heck reaction of acrolein diethyl acetal with iodo-, bromo- or chloroarenes in N,N-dimethylacetamide (DMA) using K2CO3 as base at 120°C and tetra-n-butylammonium acetate (TBAA) and KCl as additives, followed by acid workup. In the case of 3-arylpropanoate esters the corresponding arylation of acrolein diethyl acetal with iodoarenes can be performed at 90°C in aqueous DMA using (dicylohexyl)methylamine as base, whereas for bromoarenes the reaction has to be performed at 120°C using tetra-n-butylammonium bromide (TBAB) as additive. Alternatively, this process can be performed under microwave irradiation. These couplings take place in good yields and with lower catalyst loading than with palladium(II) acetate as well as in shorter reaction times and with lower excess of acrolein diethyl acetal.
- Nájera, Carmen,Botella, Luis
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p. 9688 - 9695
(2007/10/03)
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- 3-arylpropanoate esters through the palladium-catalyzed reaction of aryl halides with acrolein diethyl acetal
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The reaction of aryl halides with acrolein diethyl acetal in the presence of Pd(OAc)2, n-Bu3N, and n-Bu4NCl in DMF at 90°C affords ethyl 3-arylpropanoates. A variety of functional groups are tolerated in the aryl halides, including ether, aldehyde, ketone, ester, nitrile, and nitro groups. ortho-Substituents do not hamper the reaction. 3-Arylpropanoate esters were isolated in good to excellent yields with many neutral, electron-rich and electron-poor aryl iodides and electron-poor aryl bromide. Neutral and electron-rich aryl bromides gave the desired ester in moderate yields.
- Battistuzzi, Gianfranco,Cacchi, Sandro,Fabrizi, Giancarlo,Bernini, Roberta
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p. 1133 - 1136
(2007/10/03)
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- ARYLATION AND VINYLATION OF 2-CARBOETHOXYETHYLZINC IODIDE AND 3-CARBOETHOXYPROPYLZINC IODIDE CATALYZED BY PALLADIUM
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By the palladium catalysis 2-carboethoxyethylzinc iodide reacts with aryl iodides and vinyl iodides or triflates to provide the coupling products (ethyl 3-arylpropionates and ethyl 4-pentenoates, respectively) in satisfactory yields.The similar coupling reaction is observed for the reaction with 3-carboethoxypropylzinc iodide.
- Tamaru, Y.,Ochiai, H.,Nakamura, T.,Yoshida, Z.
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p. 955 - 958
(2007/10/02)
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