- 8-Hydroxyquinolin-2(1H)-one analogues as potential β2-agonists: Design, synthesis and activity study
-
β2-Agonists that bind to plasmalemmal β2-adrenoceptors causing cAMP accumulation are widely used as bronchodilators in chronic respiratory diseases. Here, we designed and synthesized a group of 8-hydroxyquinolin-2(1H)-one analogues and studied their β2-agonistic activities with a cellular cAMP assay. Compounds B05 and C08 were identified as potent (EC50 2-agonists among the compounds tested. They behaved as partial β2-agonists in non-overexpressed HEK293 cells, and possessed rapid smooth muscle relaxant actions and long duration of action in isolated guinea pig tracheal strip preparations. In summary, B05 and C08 are β2-agonists with potential applicability in chronic respiratory diseases.
- Xing, Gang,Zhi, Zhengxing,Yi, Ce,Zou, Jitian,Jing, Xuefeng,Yiu-Ho Woo, Anthony,Lin, Bin,Pan, Li,Zhang, Yuyang,Cheng, Maosheng
-
-
- Shuttle arylation by Rh(I) catalyzed reversible carbon–carbon bond activation of unstrained alcohols
-
The advent of transfer hydrogenation and borrowing hydrogen reactions paved the way to manipulate simple alcohols in previously unthinkable manners and circumvented the need for hydrogen gas. Analogously, transfer hydrocarbylation could greatly increase the versatility of tertiary alcohols. However, this reaction remains unexplored because of the challenges associated with the catalytic cleavage of unactivated C–C bonds. Herein, we report a rhodium(I)-catalyzed shuttle arylation cleaving the C(sp2)–C(sp3) bond in unstrained triaryl alcohols via a redox-neutral β-carbon elimination mechanism. A selective transfer hydrocarbylation of substituted (hetero)aryl groups from tertiary alcohols to ketones was realized, employing benign alcohols as latent C-nucleophiles. All preliminary mechanistic experiments support a reversible β-carbon elimination/migratory insertion mechanism. In a broader context, this novel reactivity offers a new platform for the manipulation of tertiary alcohols in catalysis.
- Lutz, Marius D.R.,Gasser, Valentina C.M.,Morandi, Bill
-
supporting information
p. 1108 - 1119
(2021/04/19)
-
- Highly productive α-alkylation of ketones with alcohols mediated by an Ir-oxalamidato/solid base catalyst system
-
An Ir-oxalamidato complex in combination with a solid base (e.g., magnesium aluminometasilicate/Ca(OH)2) significantly improved the catalyst productivity in α-alkylation of methyl ketones with primary alcohols. Optimization through systematic variation of the oxalamidato ligand led to a practical turnover number (TON) of 10 000.40 000.
- Maeda, Hironori,Nara, Hideki,Shimizu, Hideo
-
supporting information
p. 2772 - 2779
(2020/12/29)
-
- Ruthenium [NNN] and [NCN]-type pincer complexes with phosphine coligands: synthesis, structures and catalytic applications
-
A series of ruthenium [NNN]- or [NCN]-type complexes (3–7) bearing PPh3 ancillary ligands have been synthesized from pyridine- or phenylene-bridged bis(triazoles) 1 and 2. In the case of [NNN]-pincer complex 3, an unusual and unexpected cis-orientation adopted by two sterically demanding PPh3 ligands was observed, and such configuration proved to be unchanged in solution for a long time. By contrast and as expected, the two phosphines are found to be trans to each other in the case of [NCN]-type pincer complex 4, but an oxidation of RuII center to RuIII occurred. Complex cis-3 underwent ligand exchanges leading to the formations of diphosphine derivatives 5 and 6. As a representative, cis-3 was treated with the base in isopropanol affording a mixture of Ru–hydrido complexes with various phosphine binding modes, one of which (trans-7) bearing two trans-standing phosphines has been successfully isolated and fully characterized. The catalytic performances of all newly synthesized Ru complexes have been examined and compared in transfer hydrogenations of ketones and enones, in which mono-phosphine complexes proved to be significantly superior to their diphosphine counterparts. The catalytic process proved to involve Ru–H key intermediates, but the trans-oriented Ru–H species is unlikely to be the main catalytic contributor. In particular, the best performer cis-3 exhibits high chemoselectivity in certain cases catalyzing α,β-unsaturated ketones, whose behavior is quite different compared to most precedents.
- Zhang, Bo,Wang, Haiying,Yan, Xuechao,Duan, Yu-Ai,Guo, Shuai,Luo, Fei-Xian
-
-
- Iron powder and tin/tin chloride as new reducing agents of Meerwein arylation reaction with unexpected recycling to anilines
-
Simple and rapid route for Meerwein arylation reaction using iron powder or a mixture of tin/tin chloride has been developed. In the presence of iron powder, different aryl diazonium salts reacted with methyl vinyl ketone, acrylates, and isopropenyl acetate. Production of oximes was detected as the main product with acrylates or in a mixture with β-aryl methyl ketones in the case of methyl vinyl ketone. The in situ produced HNO2 from an excess of NaNO2/HCl was trapped by alkyl aryl radical to form oximes in the E configuration form. The presence of tin/tin chloride mixture in the reaction of the aryl diazonium salts with methyl vinyl ketone produced Michael products along with β-aryl methyl ketones. The predicted α-aryl methyl ketones from the reaction of isopropenyl acetate with the diazotized anilines were obtained using iron or tin/tin chloride mixture.
- Abdelwahab, Ahmed B.,El-Sawy, Eslam R.,Kirsch, Gilbert
-
supporting information
p. 526 - 538
(2020/01/08)
-
- Iridium-Catalyzed Alkene-Selective Transfer Hydrogenation with 1,4-Dioxane as Hydrogen Donor
-
The iridium-catalyzed transfer hydrogenation of alkenes using 1,4-dioxane as a hydrogen donor is described. The use of 1,2-bis(dicyclohexylphosphino)ethane (DCyPE), featuring bulky and highly electron-donating properties, led to high catalytic activity. A polystyrene-cross-linking bisphosphine PS-DPPBz produced a reusable heterogeneous catalyst. These homogeneous and heterogeneous protocols achieved chemoselective transfer hydrogenation of alkenes over other potentially reducible functional groups such as carbonyl, nitro, cyano, and imino groups in the same molecule.
- Zhang, Deliang,Iwai, Tomohiro,Sawamura, Masaya
-
supporting information
p. 5867 - 5872
(2019/08/26)
-
- Methanol as hydrogen source: Chemoselective transfer hydrogenation of α,β-unsaturated ketones with a rhodacycle
-
Methanol is a safe, economic and easy-to-handle hydrogen source. It has rarely been used in transfer hydrogenation reactions, however. We herein report that a cyclometalated rhodium complex, rhodacycle, catalyzes highly chemoselective hydrogenation of α,β-unsaturated ketones with methanol as the hydrogen source. A wide variety of chalcones, styryl methyl ketones and vinyl methyl ketones, including sterically demanding ones, were reduced to the saturated ketones in refluxing methanol in a short reaction time, with no need for inter gas protection, and no reduction of the carbonyl moieties was observed. The catalysis described provides a practically easy and operationally safe method for the reduction of olefinic bonds in α,β-unsaturated ketone compounds.
- Aboo, Ahmed H.,Begum, Robina,Zhao, Liangliang,Farooqi, Zahoor H.,Xiao, Jianliang
-
p. 1795 - 1799
(2019/11/11)
-
- Palladium Catalysis for Aerobic Oxidation Systems Using Robust Metal–Organic Framework
-
Described here is a new and viable approach to achieve Pd catalysis for aerobic oxidation systems (AOSs) by circumventing problems associated with both the oxidation and the catalysis through an all-in-one strategy, employing a robust metal–organic framework (MOF). The rational assembly of a PdII catalyst, phenanthroline ligand, and CuII species (electron-transfer mediator) into a MOF facilitates the fast regeneration of the PdII active species, through an enhanced electron transfer from in situ generated Pd0 to CuII, and then CuI to O2, trapped in the framework, thus leading to a 10 times higher turnover number than that of the homogeneous counterpart for Pd-catalyzed desulfitative oxidative coupling reactions. Moreover, the MOF catalyst can be reused five times without losing activity. This work provides the first exploration of using a MOF as a promising platform for the development of Pd catalysis for AOSs with high efficiency, low catalyst loading, and reusability.
- Li, Jiawei,Liao, Jianhua,Ren, Yanwei,Liu, Chi,Yue, Chenglong,Lu, Jiaming,Jiang, Huanfeng
-
supporting information
p. 17148 - 17152
(2019/11/03)
-
- Catalytic Wacker-type Oxidations Using Visible Light Photoredox Catalysis
-
A combined palladium/photoredox catalytic system for the efficient oxidation of terminal olefins to the corresponding methyl ketones is presented. The interplay of air, water, and light leads to a protocol in which the stoichiometric oxidants required for oxidative palladium catalysis are substituted with catalytic, single-electron transfer processes. Detailed mechanistic investigations revealed the role of the key components, in situ generated species, and catalysts. A broad range of substrates was examined in homogeneous as well as heterogeneous photoredox protocols, delivering the desired products in good yields.
- Ho, Yee Ann,Paffenholz, Eva,Kim, Hyun Jin,Orgis, Benjamin,Rueping, Magnus,Fabry, David C.
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p. 1889 - 1892
(2019/03/17)
-
- D-AMINO ACID OXIDASE INHIBITORS AND THERAPEUTIC USES THEREOF
-
The present invention relates to compounds of Formula (I): or a pharmaceutically acceptable salt thereof, wherein: each of A, B, C, D, and E, independently, is C, N, N—H, O, S, or absent is a single bond or a double bond; each of X, Y, and Z, independentl
- -
-
Paragraph 0169
(2019/04/29)
-
- Palladium-Catalyzed Synthesis of β,β-Diaryl α,β-Unsaturated Ketones
-
We herein describe a versatile palladium-catalyzed synthesis of β,β-diaryl α,β-unsaturated ketones. A broad range of aryl halides react with β-arylbutanones to afford biologically useful, symmetrical and unsymmetrical ketones. The use of 4,5-diazafluoren-9-one and oxygen makes this one-pot reaction more applicable. A plausible mechanism involving palladium-catalyzed oxidative Heck-type cross-coupling is also proposed.
- Zheng, Yi-Lin,Xiao, Li,Xie, Qiong,Shao, Li-Ming
-
p. 1455 - 1465
(2019/03/07)
-
- Mild Chemoenzymatic Oxidation of Allylic sec-Alcohols. Application to Biocatalytic Stereoselective Redox Isomerizations
-
The design of catalytic oxidative methodologies in aqueous medium under mild reaction conditions and using molecular oxygen as final electron acceptor represents a suitable alternative to the traditional oxidative transformations. These methods are especially relevant if other functionalities that can be oxidized are present within the same molecule, as in the case of allylic alcohols. Herein we apply a simple chemoenzymatic system composed of the laccase from Trametes versicolor and 2,2,6,6-tetramethylpiperidinyloxy radical (TEMPO) to oxidize a series of racemic allylic sec-alcohols into the corresponding α,β-unsaturated ketones. Afterward, these compounds react with different commercially available ene-reductases to afford the corresponding saturated ketones. Remarkably, in the case of trisubstituted alkenes, the bioreduction reaction occurred with high stereoselectivity. Overall, a bienzymatic one-pot two-step sequential strategy has been described with respect to the synthesis of saturated ketones starting from racemic allylic alcohols, thus resembling the metal-catalyzed redox isomerizations of these derivatives that have been previously reported in the literature.
- Martínez-Montero, Lía,Gotor, Vicente,Gotor-Fernández, Vicente,Lavandera, Iván
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p. 2413 - 2419
(2018/03/13)
-
- Hydrogen-transfer reduction of α,β-unsaturated carbonyl compounds catalyzed by naphthyridine-functionalized N-heterocyclic carbene complexes
-
Substitution of silver complex of 2-chloro-7-(mesitylimidazolylidenylmethyl)naphthyridine (NpNHC) with palladium(II), rhodium(I) and iridium(I) metal precursors provided [Pd(C,N-NpNHC)(η3-allyl)](BF4) (5), RhCl(COD)(C-NpNHC) (6a) and IrCl(COD)(C-NpNHC) (6b), respectively. Abstraction of chloride from 6a and 6b with AgBF4 provided the chelation complexes [Rh(COD)(C,N-NpNHC)](BF4) (7a) and Ir(COD)(C,N-NpNHC)(BF4) (7b), respectively. All complexes were characterized using NMR and elemental analyses and the structural details of 5 and 6a were further confirmed using X-ray crystallography. In catalytic activity studies, complex 5 was found to be an effective catalyst in the hydrogen-transfer reduction of α,β-unsaturated carbonyl compounds into the corresponding saturated carbonyl compounds.
- Huang, Hsiao-Ching,Ramanathan, Mani,Liu, Yi-Hong,Peng, Shie-Ming,Liu, Shiuh-Tzung
-
-
- Synthesis and neuroprotective evaluation of (E)-3,4-dihydroxystyryl p-substituted-phenethyl ketone derivatives against inflammatory and oxidative injury
-
(E)-3,4-dihydroxystyryl p-substituted-phenethyl ketones and their 3,4-diacetylated derivatives were synthesized and examined their neuroprotective activities to further study the effect of p-substituents on the aromatic ring. The results revealed that steric hindrance effect of p-substituents has impact on neuroprotective activities against inflammatory and oxidative injury. Introduction of the bulkier groups are more beneficial to improve the neuroprotective activities than smaller groups. Compounds (4–5h, 4–5i and 4–5e) with p-substituted trifluoromethyl, isopropyl and t-butyl groups exhibited the best effects among all the target compounds.
- Cheng, Can,Ning, Xianling,Luo, Yongming,Tian, Chao,Wang, Xiaowei,Guo, Ying,Liu, Junyi,Zhang, Zhili
-
p. 1678 - 1685
(2016/07/30)
-
- Switchable asymmetric bio-epoxidation of α,β-unsaturated ketones
-
Efficient asymmetric bio-epoxidation of electron-deficient α,β-unsaturated ketones was realized via a tandem reduction-epoxidation-dehydrogenation cascade, which proceeds in a switchable manner to afford either chiral epoxy ketones or allylic epoxy alcoho
- Liu, Yu-Chang,Wu, Zhong-Liu
-
supporting information
p. 1158 - 1161
(2016/01/15)
-
- AUTOTAXIN INHIBITORS
-
The present invention relates to compounds of formula (I): wherein R1, R2, R3, R4a, R4b, R4C, R4d, L, A, Q, W and HET are each as defined herein. The compounds of the present inv
- -
-
Paragraph 00371; 00372
(2016/09/22)
-
- Sunlight-driven trifluoromethylation of olefinic substrates by photoredox catalysis: A green organic process
-
The principles and utility of photoredox catalysis in organic synthesis are described. After a brief description of the features of the two types of catalytic photoredox processes following the reductive quenching cycle (RQC) and the oxidative quenching cycle (OQC), the discussion is focused on organic transformations based on OQC, in particular the trifluoromethylation of olefinic substrates with electrophilic trifluoromethylating reagents furnishing solvolytic addition products and substitution products. It is concluded that catalytic photoredox systems are green from the point of view of harmfulness, safety, and energy source (visible light, including sunlight). Future prospects of photoredox catalysis will be also discussed.
- Akita, Munetaka,Koike, Takashi
-
p. 742 - 751
(2015/07/15)
-
- Copper catalyzed oxygen assisted C(CNOH)-C(alkyl) bond cleavage: A facile conversion of aryl/aralkyl/vinyl ketones to aromatic acids
-
A novel copper-catalyzed aerobic oxidative C(NOH)-C(alkyl) bond cleavage reaction of aryl/aralkyl/vinyl ketones for the synthesis of aromatic/acrylic acids is described. A series of ketones having aryl/aralkyl/vinyl at the one end and methyl to any higher alkyl at the other end can be selectively cleaved and converted into the corresponding acids via oxime intermediates.
- Sathyanarayana, Pochampalli,Ravi, Owk,Muktapuram, Prathap Reddy,Bathula, Surendar Reddy
-
supporting information
p. 9681 - 9685
(2015/09/28)
-
- Enantioselective oxidation of secondary alcohols by Candida parapsilosis ATCC 7330
-
Optically pure allylic alcohols and 4-phenylbutan-2-ols were prepared by oxidative kinetic resolution using whole cells of Candida parapsilosis ATCC 7330. Only the 'S' enantiomer is selectively oxidized to the corresponding keto compound (yield, 37-46%) leaving the 'R' alcohol (yield, 37-52% and ee 46 to >99%). The biocatalytic method is carried out under mild conditions at 20°C, pH 6.5 in phosphate buffer.
- Sivakumari, Thakkellapati,Preetha, Radhakrishnan,Chadha, Anju
-
p. 2257 - 2262
(2014/01/06)
-
- Iridium(I)-catalyzed regioselective C-H activation and hydrogen-isotope exchange of non-aromatic unsaturated functionality
-
Isotopic labelling is a key technology of increasing importance for the investigation of new C-H activation and functionalization techniques, as well as in the construction of labelled molecules for use within both organic synthesis and drug discovery. Herein, we report for the first time selective iridium-catalyzed C-H activation and hydrogen-isotope exchange at the β-position of unsaturated organic compounds. The use of our highly active [Ir(cod)(IMes)(PPh3)][PF6] (cod = 1, 5-cyclooctadiene) catalyst, under mild reaction conditions, allows the regioselective β-activation and labelling of a range of α, β-unsaturated compounds with differing steric and electronic properties. This new process delivers high levels of isotope incorporation over short reaction times by using low levels of catalyst loading.
- Kerr, William J.,Mudd, Richard J.,Paterson, Laura C.,Brown, Jack A.
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p. 14604 - 14607
(2015/03/04)
-
- Synthesis of β-aryl ketones by heck arylation of allylic alcohols catalysed by a MCM-41-supported bidentate nitrogen palladium complex
-
The Heck arylation reaction of aryl iodides with allylic alcohols catalysed by an mesoporous silica (MCM-41)-supported bidentate nitrogen palladium complex [MCM-41-2N-Pd(OAc)2] proceeded smoothly in the presence of tetrabutylammonium chloride (TBAC) in DMF to afford β-aryl ketones in good to excellent yields. This heterogeneous palladium catalyst can be recovered by simple filtration and reused several times without any decrease in activity.
- Huang, Yixiang,Wang, Pingping,Liu, Jiaqin,Cai, Mingzhong
-
p. 333 - 336
(2013/07/26)
-
- Malononitrile-assisted highly chemoselective bismuth triflate catalyzed conjugate reduction of α,β-unsaturated ketones
-
A very simple, direct, bismuth-catalyzed conjugate reduction protocol that allows for the catalytic regioselective formation of substituted ketones from enones under mild conditions has been developed. We have shown for the first time that the combined poly(methylhydro)siloxane-malononitrile system can serve as an efficient reductant/reagent in 1,4-conjugate reduction of enones. The regioselectivity, efficiencies, and experimental simplicity of the present method complements the more complex methods previously employed in copper or palladium-catalyzed reduction. This method should prove attractive because of its mild reaction conditions and the interesting chemistry of combining the use of poly(methylhydro)siloxane and malononitrile for selective reduction. Copyright
- Shang, Jun-Yan,Li, Fei,Bai, Xing-Feng,Jiang, Jian-Xiong,Yang, Ke-Fang,Lai, Guo-Qiao,Xu, Li-Wen
-
supporting information; experimental part
p. 2809 - 2815
(2012/06/18)
-
- LYSOPHOSPHATIDIC ACID RECEPTOR ANTAGONISTS AND USES THEREOF
-
Described herein are compounds that are antagonists of lysophosphatidic receptor(s). Also described are pharmaceutical compositions and medicaments that include the compounds described herein, as well as methods of using such antagonists, alone and in combination with other compounds, for treating LPA-dependent or LPA-mediated conditions or diseases.
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Page/Page column 149
(2012/06/30)
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- Stereospecific intramolecular C-H amination of 1-aza-2-azoniaallene salts
-
We report that 1-aza-2-azoniaallene salts, generated from α-chloroazo compounds by treatment with halophilic Lewis acids, participate in intramolecular C-H amination reactions to provide pyrazoline products in good to excellent yield. This intramolecular amination occurs readily at both benzylic and tertiary aliphatic positions and proceeds at an enantioenriched chiral center without loss of enantiomeric excess. A competition reaction shows that insertion occurs more readily at an electron-rich benzylic position than an electron-deficient one. These observations are consistent with the 1-aza-2-azoniaallene intermediate reacting as a nitrenium-like ion by a concerted insertion mechanism.
- Bercovici, Daniel A.,Brewer, Matthias
-
supporting information; body text
p. 9890 - 9893
(2012/08/08)
-
- Novel diarylheptanoids as inhibitors of TNF-α production
-
Synthesis and anti-inflammatory activity of novel diarylheptanoids [5-hydroxy-1-phenyl-7-(pyridin-3-yl)-heptan-3-ones and 1-phenyl-7-(pyridin-3-yl) hept-4-en-3-ones] as inhibitors of tumor necrosis factor-α (TNF-α) production is described in the present article. The key reactions involve the formation of a β-hydroxyketone by the reaction of substituted 4-phenyl butan-2-ones with pyridine-3-carboxaldehyde in presence of LDA and the subsequent dehydration of the same to obtain the α,β-unsaturated ketones. Compounds 4i, 5b, 5d, and 5g significantly inhibit lipopolysaccharide (LPS)-induced TNF-α production from human peripheral blood mononuclear cells in a dose-dependent manner. Of note, the in vitro TNF-α inhibition potential of 5b and 5d is comparable to that of curcumin (a naturally occurring diarylheptanoid). Most importantly, oral administration of 4i, 5b, 5d, and 5g (each at 100 mg/kg) but not curcumin (at 100 mg/kg) significantly inhibits LPS-induced TNF-α production in BALB/c mice. Collectively, our findings indicate that these compounds may have potential therapeutic implications for TNF-α-mediated auto-immune/inflammatory disorders.
- Dhuru, Sameer,Bhedi, Dilip,Gophane, Dnyaneshwar,Hirbhagat, Kiran,Nadar, Vijaya,More, Dattatray,Parikh, Sapna,Dalal, Roda,Fonseca, Lyle C.,Kharas, Firuza,Vadnal, Prashant Y.,Vishwakarma, Ram A.,Sivaramakrishnan
-
supporting information; experimental part
p. 3784 - 3787
(2011/07/31)
-
- Titanocene-catalyzed conjugate reduction of αβ-unsaturated carbonyl derivatives
-
"Chemical Equation Presented" A titanocene-catalyzed conjugate reduction of αβ-unsaturated carbonyl derivatives has been developed. A series of carbonyl compounds including aldehydes, ketones, esters, and amides proved viable in the reduction process providing an efficient, chemoselective method for the catalytic reduction of unsaturated carbonyl derivatives.
- Ashfeld, Brandon L.,Kosal, Andrew D.
-
scheme or table
p. 44 - 47
(2010/03/03)
-
- Improving the atom efficiency of the wittig reaction by a "waste as catalyst/Co-catalyst" strategy
-
(Figure Presented) Waste not want not: Reported is a strategy to improve the atom economy of the Wittig reaction by using it in tandem reactions that directly employ the wastePh3PO as an in-situ-generated Lewis base catalyst/co-catalyst in the next step (see scheme).
- Cao, Jun-Jie,Zhou, Feng,Zhou, Jian
-
supporting information; experimental part
p. 4976 - 4980
(2010/09/08)
-
- Chemoselective conjugate reduction of α,β-unsaturated ketones catalyzed by rhodium amido complexes in aqueous media
-
Although a notable feature of Noyori's Ru-TsDPEN complex is that the transfer hydrogenation reaction is highly chemoselective for the C-O functional group and tolerant of alkenes, our early report indicated that the chemoselectivity could be switched from C-O to C-C bonds in the transfer hydrogenation of activated α,β-unsaturated ketones. Now we have found that a variety of α,β-unsaturated ketones, even without other electron-withdrawing functional groups, could be reduced on the alkenic double bonds with high selectivities employing amido-rhodium hydride complex in aqueous media, and up to 100% chemoselectivity has been achieved. It is notable that the chemoselectivity was improved significantly on going from organic solvent to water. Moreover, a 1,4-addition mechanism has been proposed on the basis of the corresponding experimental details and computational analysis.
- Li, Xuefeng,Li, Liangchun,Tang, Yuanfu,Zhong, Ling,Cun, Linfeng,Zhu, Jin,Liao, Jian,Deng, Jingen
-
experimental part
p. 2981 - 2988
(2010/07/05)
-
- Carbonylative 1,4-addition of potassium aryltrifluoroborates to vinyl ketones
-
Potassium aryltrifluoroborates have proven to be useful reagents for the carbonylative aroylation of vinyl ketones; this study broadens the scope of potassium aryltrifluoroborates in homogeneous catalysis and shows that the solvent can act as the proton s
- Sauthier, Mathieu,Lamotte, Nicolas,Dheur, Julien,Castanet, Yves,Mortreux, Andre
-
experimental part
p. 969 - 971
(2010/08/21)
-
- Rhodium-catalyzed conjugate addition of Sb-aryl-1,5-azastibocines to α,β-unsaturated carbonyl compounds
-
Rhodium-catalyzed conjugate addition of Sb-aryl-1,5-azastibocines to α,β-unsaturated carbonyl compounds is described. The rhodium-catalyzed reaction was carried out in aqueous N-methy-2-pyrrolidinone (NMP) to give 1,4-conjugate adduct exclusively, while t
- Kakusawa, Naoki,Yasuike, Shuji,Kurita, Jyoji
-
experimental part
p. 1269 - 1283
(2010/10/03)
-
- SUBSTITUTE 1, 6-NAPHTHYRIDINES FOR USE AS SCD INHIBITORS
-
The present invention relates to substituted tetrahydronaphthyridine (THN) compounds of the formula (I) and salts thereof, to pharmaceutical compositions containing them and their use in medicine. In particular, the invention relates to compounds for inhibiting SCD activity.
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-
Page/Page column 37
(2009/06/27)
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- Rhodium catalyzed 1,4-conjugate addition of 1,5-azastibocines with electron deficient olefins
-
The rhodium-catalyzed reaction of Sb-aryl-1,5-azastibocines with α,β-unsaturated ketones and esters is described. Exclusive formation of 1,4-conjugate adduct was achieved in aqueous NMP (N-methyl-2-pyrrolidinone) in the presence of 5 mol% of [RhCl(cod)]s
- Kakusawa, Naoki,Kurita, Jyoji
-
scheme or table
p. 1502 - 1504
(2009/10/24)
-
- Rhodium fluoroapatite catalyzed conjugate addition of arylboronic acids to α,β-unsaturated carbonyl compounds
-
Rhodium fluoroapatite (RhFAP) is an efficient catalyst for conjugate addition of organoboron reagents to α,β-unsaturated carbonyl compounds. A variety of arylboronic acids and α,β-unsaturated carbonyl compounds were converted to the corresponding conjugat
- Kantam, Mannepalli Lakshmi,Subrahmanyam, Vura Bala,Kumar, Kota Balaji Shiva,Venkanna, Gopaladasu T.,Sreedhar, Bojja
-
scheme or table
p. 1947 - 1953
(2009/02/07)
-
- CHIRALLY PURE ISOMERS OF ITRACONAZOLE AND INHIBITORS OF LANOSTEROL 14A- DEMETHYLASE FOR USE AS ANGIOGENESIS INHIBITORS
-
Described herein are methods of inhibiting angiogenesis, and treating or preventing a disease or disorder (or symptoms thereof) associated with angiogenesis, wherein an anti-angiogenesis compound is administered to a subject.
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Page/Page column 54
(2008/12/04)
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- Pd/C-catalyzed chemoselective hydrogenation in the presence of diphenylsulfide
-
A Pd/C-catalyzed chemoselective hydrogenation using diphenylsulfide as a catalyst poison has been developed. This methodology selectively hydrogenates olefin and acetylene functionalities without hydrogenolysis of aromatic carbonyls and halogens, benzyl esters, and N-Cbz protective groups.
- Mori, Akinori,Miyakawa, Yumi,Ohashi, Eri,Haga, Tomoko,Maegawa, Tomohiro,Sajiki, Hironao
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p. 3279 - 3281
(2007/10/03)
-
- Chemoselective hydrogenation method catalyzed by Pd/C using diphenylsulfide as a reasonable catalyst poison
-
While Pd/C is one of the most useful catalysts for hydrogenation, the high catalyst activity of Pd/C causes difficulty in its application to chemoselective hydrogenation between different types of reducible functionalities. In order to achieve chemoselective hydrogenation using Pd/C, we investigated catalyst poison as a controller of the catalyst activity. We found that the addition of Ph2S (diphenylsulfide) to the Pd/C-catalyzed hydrogenation reaction mixture led to reasonable deactivation of Pd/C. By the use of the Pd/C-Ph2S catalytic system, olefins, acetylenes, and azides can be selectively reduced in the coexistence of aromatic carbonyls, aromatic halides, cyano groups, benzyl esters, and N-Cbz (benzyloxycarbonyl) protecting groups. The present method is promising as a general and practical chemoselective hydrogenation process in synthetic organic chemistry.
- Mori, Akinori,Mizusaki, Tomoteru,Miyakawa, Yumi,Ohashi, Eri,Haga, Tomoko,Maegawa, Tomohiro,Monguchi, Yasunari,Sajiki, Hironao
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p. 11925 - 11932
(2007/10/03)
-
- Pyrrole and pyrazole DAAO inhibitors
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Methods for increasing D-Serine concentration and reducing concentration of the toxic products of D-Serine oxidation, for enhancing learning, memory and/or cognition, or for treating schizophrenia, Alzheimer's disease, ataxia or neuropathic pain, or preventing loss in neuronal function characteristic of neurodegenerative diseases involve administering to a subject in need of treatment a therapeutically effective amount of a compound of formula I, or a pharmaceutically acceptable salt or solvate thereof: wherein R1 and R2 are independently selected from hydrogen, halo, nitro, alkyl, acyl, alkylaryl, and XYR5; or R1 and R2, taken together, form a 5, 6, 7 or 8-membered substituted or unsubstituted carbocyclic or heterocyclic group; X and Y are independently selected from O, S, NH, and (CR6R7)n; R3 is hydrogen, alkyl or M+; M is aluminum, calcium, lithium, magnesium, potassium, sodium, zinc ion or a mixture thereof; Z is N or CR4; R4 is from selected from hydrogen, halo, nitro, alkyl, alkylaryl, and XYR5; R5 is selected from aryl, substituted aryl, heteroaryl and substituted heteroaryl; R6 and R7 are independently selected from hydrogen and alkyl; n is an integer from 1 to 6; at least one of R1, R2 and R4 is other than hydrogen; and at least one of X and Y is (CR6R7)n. D-serine or cycloserine may be coadministered along with the compound of formula I.
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Page/Page column 30
(2008/06/13)
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- New synthesis of 1,4-diketones via rhodium-catalysed 1,4 carbonylative addition of arylboronic acids to α,β-unsaturated ketones
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The reaction of various arylboronic acids with α,β-unsaturated ketones under CO pressure and in the presence of rhodium catalyst yields 1,4-diketones.
- Sauthier, Mathieu,Castanet, Yves,Mortreux, Andre
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p. 1520 - 1521
(2007/10/03)
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- Nickel-catalyzed cross-couplings of organosilicon reagents with unactivated secondary alkyl bromides
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A metal-catalyzed cross-coupling of organosilicon compounds with alkyl halides has been developed. Noteworthy attributes of the method are its scope (secondary electrophiles), its high functional-group compatibility, and the air stability of the catalyst components. Copyright
- Powell, David A.,Fu, Gregory C.
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p. 7788 - 7789
(2007/10/03)
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- Amphiphilic Resin-Supported Rhodium-Phosphine Catalysts for C-C Bond Forming Reactions in Water
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Amphiphilic resin-supported rhodium-phosphine complexes were prepared on polystyrene-poly(ethylene glycol) graft co-polymer (1% DVB cross-linked) beads. The immobilized rhodium complexes exhibited high catalytic activity in water to promote hydroformylation of 1-alkenes, [2+2+2] cyclotrimerization of internal alkynes forming benzene rings, and 1,4-addition of arylboronic acids.
- Uozumi, Yasuhiro,Nakazono, Maki
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p. 274 - 277
(2007/10/03)
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- Palladium-catalyzed arylation of allylic alcohols with aryl iodides in water
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Palladium-catalyzed arylation of allylic alcohols with aryl iodides are shown to occur in the presence of sodium bicarbonate and tetra-n-butylammonium chloride in pure water using palladium acetate as catalyst. β-aromatic carbonyl compounds are obtained in good yields.
- Zhao,Cai,Hu,Song
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p. 3665 - 3669
(2007/10/03)
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- Dynamic kinetic resolution of allylic alcohols mediated by ruthenium- and lipase-based catalysts.
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An enzyme-metal combo reaction has been developed for the dynamic kinetic resolution of allylic alcohols in which racemic substrates are transformed by a lipase and a ruthenium complex in the presence of an acyl donor to allylic acetates of high optical purity in over 80% yield.
- Lee,Huh,Kim,Jung,Koh,Park
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p. 2377 - 2379
(2007/10/03)
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- Selectivity in palladium catalyzed arylation: Synthetic application leading to aromatized ionone natural products
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The selectivity in aromatic substitution vs conjugate addition during palladium catalyzed reactions has been controlled simply by changing the base. These reaction conditions have been applied to the syntheses of aromatized β-ionone natural products 1 and its dihydroderivatives 7.
- Hagiwara, Hisahiro,Eda, Yasushi,Morohashi, Kimie,Suzuki, Toshio,Ando, Masayoshi,Ito, Nobuhiko
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p. 4055 - 4058
(2007/10/03)
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- Palladium(II)-Catalyzed Conjugate Addition of Aromatics to α,β-Unsaturated Ketones and Aldehydes with Arylantimony Compounds
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Triarylstibines react with α,β-unsaturated ketones and aldehydes in acetic acid at room temperature in the presence of AgOAc and a catalytic amount of Pd(OAc)2 to afford the conjugate addition products (the formal hydroarylated compounds to an olefinic part) in good yields. In contrast, diarylantimony chlorides, arylantimony dichlorides, and diphenylantimony acetate react with the enones and enals even in the absence of AgOAc to afford the same products in higher yields compared with those from triarylstibines. These are new C-C bond-forming reactions using arylantimony(III) compounds in which the formation of a palladium enolate or a trivalent antimony enolate is proposed as an intermediate.
- Cho, Chan Sik,Motofusa, Shin-Ichi,Ohe, Kouichi,Uemura, Sakae
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p. 2341 - 2348
(2007/10/03)
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- Steric, Polar, and Resonace Effects in Reactivity and Regioselectivity of Aryl Radical Addition to α,β-Unsaturated Carbonyl Compounds
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Free-radical decomposition of diazonium salts by titanous salts in the presence of olefins conjugated with carbonyl groups leads to reductive arylation or arylation and diazo coupling of the radical adduct, depending on the orientation of the aryl radical addition (β or α).The absolute rate constants of the addition (107 - 108 M-1s-1 at 5 deg C) were determined by comparison with the rate of the iodine abstraction by aryl radicals from isopropyl iodide.The obtained data of the addition rates to the β position correlate well with the Es steric parameters.The influence of the resonace stabilization of the radical adduct on the reactivity can be significant, but the regioselectivity of the addition is mainly determined by steric effects.The different fate of the α- and β-radical adducts are discussed on the basis of their different polar character.
- Citterio, Attilio,Minisci, Francesco,Vismara, Elena
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