- Iridium-catalyzed highly chemoselective and efficient reduction of nitroalkenes to nitroalkanes in water
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An iridium-catalyzed highly chemoselective and efficient transfer hydrogenation reduction of structurally diverse nitroalkenes was realized at very low catalyst loading (S/C = up to 10000 or 20?000), using formic acid or sodium formate as a traceless hydride donor in water. Excellent functionality tolerance is also observed. The turnover number and turnover frequency of the catalyst reach as high as 18?600 and 19?200 h-1, respectively. An inert atmosphere protection is not required. The reactivities of nitroalkenes are dependent on their substitution pattern, and the pH value is a key factor to accomplish the complete conversion and excellent chemoselectivity. Purification of products is achieved by simple extraction without column chromatography. The reduction procedure is facilely amplified to 10 g scale at 10?000 S/C ratio. The potential of this green reduction in enantioselective hydrogenation has been demonstrated.
- Chen, Yang,Liu, Changmeng,Xu, Dong,Xu, Jiaxi,Yang, Zhanhui
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supporting information
p. 6050 - 6058
(2021/08/23)
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- 2D-2D Nanocomposite of MoS2-Graphitic Carbon Nitride as Multifunctional Catalyst for Sustainable Synthesis of C3-Functionalized Indoles
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A nanocomposite of two-dimensional MoS2 supported on graphitic C3N4 nanosheets has been prepared by a facile ultrasonication method followed by demonstrating its ability to catalyze the synthesis of several indole derivatives. The as-prepared nanocomposite catalyst was characterized in detail by using different microscopic and spectroscopic techniques to understand its structure and physicochemical properties. Subsequently, this nanocomposite catalyst was used as a heterogeneous multifunctional catalyst to synthesize several C3-functionalized indoles in the aqueous medium. The employed strategy also provided very good catalyst recyclability and versatility for the synthesis of various precursors of medicinally significant indoles, such as serotonin, melatonin, and various β-carboline alkaloids. In addition, a natural product derivate has been prepared on the gram-scale by using this methodology. Furthermore, high atom economy (100 %) and lower E-factor (0.042) makes this strategy a sustainable approach for the synthesis of C3-functionalized indoles.
- Bahuguna, Ashish,Kumar, Ashwani,Kumar, Suneel,Chhabra, Tripti,Krishnan, Venkata
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p. 3121 - 3132
(2018/07/29)
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- Indole derivative and uses thereof
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The present invention relates to an indole derivative and uses thereof, wherein the compound and the pharmaceutical composition comprising the compound can be used for antagonizing orexin receptors. The present invention further relates to a method for preparing the compound and the pharmaceutical composition, and uses of the compound and the pharmaceutical composition in treatment or prevention of diseases associated with orexin receptors.
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- New insights into the catalytic reduction of aliphatic nitro compounds with hypophosphites under ultrasonic irradiation
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This work describes an efficient process for the reduction of nitro compounds to the corresponding amines with a catalytic amount of Pd/C (0.6 mol%), and a mixture of sodium hypophosphite and hypophosphorous acid as a reducing agent in H2O/2-MeTHF at 60 °C. The reaction was optimized under silent conditions. The conditions for the in situ production of H2 using the mixture NaH2PO2/H3PO2 were studied. The influence of ultrasonic activation was investigated both in terms of efficiency and kinetics. The reaction was shown to be efficient in water, at 70 °C with a quantitative conversion and a maximal yield in only 15 min thanks to the ultrasonic activation. Finally, ultrasound was proved to act as a physical agent of phase transfer.
- Letort,Lejeune,Kardos,Métay,Popowycz,Lemaire,Draye
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supporting information
p. 4583 - 4590
(2017/10/13)
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- Synthesis and anti-inflammatory activity of indole glucosinolates
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The nitronate and nitrovinyl methods to synthesize indole glucosinolates (GLs) have been investigated. The results were applied to generally the most prevalent natural indole glucosinolates to synthesize 4-methoxyglucobrassicin (MGB) and neo-glucobrassici
- Vo, Quan V.,Trenerry, Craige,Rochfort, Simone,Wadeson, Jenny,Leyton, Carolina,Hughes, Andrew B.
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p. 856 - 864
(2014/01/23)
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- Dissecting metabolic puzzles through isotope feeding: A novel amino acid in the biosynthetic pathway of the cruciferous phytoalexins rapalexin A and isocyalexin A
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Understanding defence pathways of plants is crucial to develop disease-resistant agronomic crops, an important element of sustainable agriculture. For this reason, natural plant defenses such as phytoalexins, involved in protecting plants against microbial pathogens, have enormous biotechnological appeal. Crucifers are economically important plants, with worldwide impact as oilseeds, vegetables of great dietetic value and even nutraceuticals. Notably, the intermediates involved in the biosynthetic pathways of unique cruciferous phytoalexins such as rapalexin A and isocyalexin A remain unknown. Toward this end, using numerous perdeuterated compounds, we have established the potential precursors of these unique phytoalexins and propose for the first time their detailed biosynthetic pathway. This pathway involves a variety of intermediates and a novel amino acid as the central piece of this complex puzzle. This work has set the stage for the discovery of enzymes and genes of the biosynthetic pathway of cruciferous phytoalexins of unique scaffolds.
- Pedras, M. Soledade C.,Yaya, Estifanos E.
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p. 1149 - 1166
(2013/03/29)
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- Total synthesis and biological activity of marine alkaloid eudistomins Y1-Y7 and their analogues
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Eudistomin Y class compounds are a series of β-carbolines which was originally isolated from a marine turnicate or ascidian near the South Korea Sea. These compounds contain bromo-substituted groups, which is one of the typical characters of marine natural products. We report herein the chemical synthesis and biological evaluation of seven new β-carboline-based metabolites, Eudistomins Y1-Y7, and their hydroxyl-methylated phenyl derivatives. Using bromo-substituted tryptamines and bromo-substituted phenylglyoxals as the key intermediates, Eudistomins Y 1-Y7 and their derivatives were synthesized via the acid-catalyzed Pictet-Spengler reaction and fully characterized by 1H- and 13C-NMR and mass spectroscopy. Biological studies revealed that all of the compounds showed moderate growth inhibitory activity against breast carcinoma cell line MDA-231 with IC50 of 15-63 μM and the inhibitory activities of hydroxyl-methylated phenyl products were higher than that of the corresponding natural products Eudistomins Y 1-Y7.
- Jin, Huijuan,Zhang, Puyong,Bijian, Krikor,Ren, Sumei,Wan, Shengbiao,Alaoui-Jamali, Moulay A.,Jiang, Tao
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p. 1427 - 1439
(2013/07/11)
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- Design and bio-evaluation of indole derivatives as potent Kv1.5 inhibitors
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Atrial fibrillation (AF) is one of the common arrhythmias that threaten human health. Kv1.5 potassium channel is reported as an efficacious and safe target for the treatment of AF. In this paper, we designed and synthesized three series of compounds through modifying the lead compound RH01617 that was screened out by the pharmacophore model we reported earlier. All of the compounds were evaluated by the whole-patch lamp technology and most of them possessed potent inhibitory activities against Kv1.5. Compounds IIIi and IIIl were evaluated for the target selectivity as well as the pharmacodynamic effects in an isolated rat model. Due to the promising pharmacological behavior, compound IIIl deserves further pharmacodynamic and pharmacokinetic evaluations.
- Guo, Xiaoke,Yang, Qian,Xu, Jing,Zhang, Li,Chu, Hongxi,Yu, Peng,Zhu, Yingying,Wei, Jinglian,Chen, Weilin,Zhang, Yaozhong,Zhang, Xiaojin,Sun, Haopeng,Tang, Yiqun,You, Qidong
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p. 6466 - 6476
(2013/10/22)
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- New approach to oximes through reduction of nitro compounds enabled by visible light photoredox catalysis
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A range of nitro compounds are smoothly reduced to their corresponding oximes under the synergistic effects of visible light irradiation, the Ru(bpy)3Cl2 photocatalyst, Hünig's base, Mg(ClO 4)2 activation, and MeCN solvent. This remarkably mild and environmentally benign protocol, when orchestrated with classical Beckmann rearrangement, enables such high-value industrial feedstock as caprolactam to be readily accessed from simple precursor nitrocyclohexane.
- Cai, Shunyou,Zhang, Shaolong,Zhao, Yaohong,Wang, David Zhigang
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supporting information
p. 2660 - 2663
(2013/07/11)
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- Visible-light-promoted C-C bond cleavage: Photocatalytic generation of iminium ions and amino radicals
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Photoscissors: Structurally variable and synthetically robust iminium ions and amino radicals species could be simultaneously generated by visible-light-promoted photoredox cleavage of the C-C bonds in simple vicinal diamine precursors under very mild reaction conditions. Copyright
- Cai, Shunyou,Zhao, Xinyang,Wang, Xinbo,Liu, Qisong,Li, Zigang,Wang, David Zhigang
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supporting information; experimental part
p. 8050 - 8053
(2012/08/29)
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- Cascade formation of isoxazoles: Facile base-mediated rearrangement of substituted oxetanes
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Give me five! Nitro compounds and oxetan-3-one react through an intriguing cascade sequence to give isoxazole-4-carbaldehydes using inexpensive reagents in a one-pot procedure (see scheme; Ms=methanesulfonyl). A variety of 3-substituted isoxazole-4-carbaldehydes were obtained in high overall yields.
- Burkhard, Johannes A.,Tchitchanov, Boris H.,Carreira, Erick M.
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p. 5379 - 5382
(2011/07/08)
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- Remarkable incorporation of the first sulfur containing indole derivative: Another piece in the biosynthetic puzzle of crucifer phytoalexins
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The first sulfur labelled compound, [2H4, 34S]indolyl-3-acetothiohydroxamic acid, is incorporated into the phytoalexins cyclobrassinin and spirobrassinin and the indole glucosinolate glucobrassicin, indicating that both bi
- Pedras, M. Soledade C.,Okinyo, Denis P. O.
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- CXCR3 ANTAGONISTS
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CXCR3 ANTAGONISTS Compounds, compositions and methods are provided that are useful in the treatment of conditions and diseases mediated by a chemokine receptor. In particular, the compounds of the invention modulate the CXCR3 chemokine receptor. The subject methods are useful for the treatment of inflammatory and immunoregulatory disorders and diseases, such as multiple sclerosis, rheumatoid arthritis and type I diabetes.
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Page/Page column 32
(2008/06/13)
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- I2-catalyzed Michael addition of indole and pyrrole to nitroolefins
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An easy and efficient method to generate indolyl nitroalkane 5 and pyrrolyl nitroalkane 7 in high yields using β-nitrostyrene and indole/pyrrole at room temperature in the presence of catalytic amount of iodine is reported. The short reaction times and hi
- Lin, Chunchi,Hsu, Jianming,Sastry,Fang, Hulin,Tu, Zhijay,Liu, Ju-Tsung,Ching-Fa, Yao
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p. 11751 - 11757
(2007/10/03)
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- Methodology for the efficient synthesis of 3,4-differentially substituted indoles. Fluoride ion-induced elimination-addition reaction of 1-triisopropylsilylgramine methiodides
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1-Triisopropylsilylgramine methiodide reacted smoothly with a variety of nucleophiles in the presence of tetrabutylammonium fluoride to give 3-substituted indoles. The 3,4-disubstituted indoles were efficiently synthesized by sequential use of 4-selective lithiation of 1-triisopropylsilylgramine and this new substitution reaction.
- Iwao, Masatomo,Motoi, Osamu
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p. 5929 - 5932
(2007/10/02)
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- Tyrosine Kinase Inhibitors. 2. Synthesis of 2,2'-Dithiobis(iH-indole-3-alkanamides) and Investigation of Their Inhibitory Activity against Epidermal Growth Factor Receptor and pp60v-src Protein Tyrosine Kinases
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A series of amide analogues of the 2,2'-dithiobis(1H-indole-3-alkanoic acid) class of tyrosine kinase inhibitors have been prepared, by reaction of 1H-indole-3-alkanamides (8) with S2Cl2, and separation of the desired disulfides from the initial mixtures of mono-, di-, and trisulfides formed. These amides were evaluated in vitro against epidermal growth factor receptor and pp60v-src protein tyrosine kinases. Inhibitory activity against EGF receptor tyrosine kinase was chain-length dependent, with the propanamides being the most effective. Hydrogen bond donor capabilities in the amide function did not appear to be necessary, with an N-benzylamide being the most potent (IC50 = 0.85 μM). Further substitution on the benzyl ring did not increase potency, and substitution in the α-position of the propanamide side chain was acceptable. A water-soluble α-NH2 derivative showed good inhibitory activity toward the enzyme, was a potent inhibitor of cell growth in fibroblasts, and selectively inhibited intracellular tyrosine phosphorylation patterns. The nonreceptor kinase pp60v-src was in general much more sensitive than EGF receptor kinase to inhibition by these compounds, but with less pronounced structure-activity relationships.
- Thompson, Andrew M.,Fry, David W.,Kraker, Alan J.,Denny, William A.
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p. 598 - 609
(2007/10/02)
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- REDUCTION OF AROMATIC NITROALKENES WITH BAKER'S YEAST
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Aromatic nitroalkenes were reduced chemoselectively with baker's yeast to give the corresponding nitroalkanes.
- Takeshita, Mitsuhiro,Yoshida, Sachiko,Kohno, Yoichiro
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p. 553 - 562
(2007/10/02)
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- Nitrones and Oxaziridines. XLVII. Intermolecular Cycloaddition of Fused Indolyl Nitrone Ring Systems
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The two dihydro-β-carboline N-oxides (6) and (18) have been prepared by reductive cyclization of 2-acetyl-3-(β-nitroethyl)indoles.These cyclic nitrones undergo 1,3-dipolar cycloaddition to alkynes to give the cycloadducts (21)-(25).Thermal rearrangement of the adduct (22) gives the indolizinoindole (27) in high yield.The X-ray crystal structure determination of the adduct (24) is reported.
- Black, David St. C.,Craig, Donald C.,Deb-Das, Renu B.,Kumar, Naresh,Wright, Timothy A.
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p. 1725 - 1742
(2007/10/02)
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- First synthesis of an indole glucosinolate
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The synthesis of glucobrassicin, the parent structure of the indole glucosinolate family, and its desulfoanalogue is described.
- Viaud,Rollin
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p. 1417 - 1418
(2007/10/02)
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- Enzymes as synthetic catalysts: Mechanistic and active-site considerations of natural and modified chymotrypsin
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This paper describes the mechanistic investigation of α-chymotrypsin and [Met192-sulfoxide]-α-chymotrypsin-catalyzed peptide synthesis in a kinetically controlled process (i.e., aminolysis) and the relative stabilities of both enzymes in differ
- West, J. Blair,Hennen, William J.,Lalonde, James L.,Bibbs, Jeffrey A.,Zhong, Ziyang,Meyer Jr., Edgar F.,Wong, Chi-Huey
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p. 5313 - 5320
(2007/10/02)
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- Intramolecular Pictet-Spengler Reaction of N-Alkoxytryptamines. 3. Stereoselective Synthesis of (-)-Debromoeudistomin L and (-)-O-Methyldebromoeudistomin E and Their Stereoisomers
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The N-hydroxytrypamines 10 and 11 were converted into the N-alkoxy derivatives 32-34 (overall yield 57-72percent) by successive protection with chloroformate providing 27 and 28, reaction with functionalized chloromethyl sulfides, and deprotection with a "naked" fluoride.Intramolecular cyclization succeeded with 33 and 34 by reduction of the methyl ester with DIBAL and treatment with TFA to give diastereomeric pairs with a slight selectivity for the trans isomer (53-81percent, cis/trans ca. 35/65).Removal of the BOC group gave debromoeudistomin L ((-)-1e), its three stereoisomers (42a,b and (+)-1e), O-methyldebromoeudistomin E ((-)-1f), and its stereomer 43.
- Hermkens, Pedro H. H.,Maarseveen, Jan H. v.,Ottenheijm, Harry C. J.,Kruse, Chris G.,Scheeren, Hans W.
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p. 3998 - 4006
(2007/10/02)
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- THE PICTET-SPENGLER REACTION OF Nb-HYDROXYTRYPTAMINES AND CYSTEINALS. I. ISOLATION OF TETRACYCLIC INTERMEDIATES AND FORMATION OF OPTICALLY ACTIVE Nb-HYDROXY-TETRAHYDRO-β-CARBOLINES
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The Pictet-Spengler(P-S) reaction of Nb-hydroxytryptamines 5 and cysteinals 6 in the presence of trifluoroacetic acid(TFA) at room temperature gave the tetracyclic compounds 7α as well as the corresponding Nb-hydroxy-β-carbolines 8.The optically active nitrones 9, isolated from the similar reaction of 5 and optically active 6, gave optically active 7α and 8.
- Liu, Jinjun,Nakagawa, Masako,Hino, Tohru
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p. 7729 - 7742
(2007/10/02)
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- SYNTHESIS OF NITROETHYLINDOLES FROM NITROVINYLINDOLES BY ALKOXYBOROHYDRIDE REDUCTION
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The reduction of substituted nitrovinylindoles to the corresponding nitroethylindoles proceeds in excellent yield, with the suppression of dimeric Michael byproducts, when an alkoxyborohydride is the reducing agent.A study of the reaction demonstrates the equivalence of preformed sodium trimethoxyborohydride and alkoxyborohydride generated in situ from excess sodium borohydride and methanol.
- Kruse, Lawrence I.,Hilbert, Eileen L.
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p. 1373 - 1377
(2007/10/02)
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- Selective mono-alkylation of carbon nucleophiles with gramine
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Mono-alkylation method of carbon nucleophiles, especially for nitroalkanes, with gramine derivatives is reported
- Somei, Masanori,Karasawa, Yoshio,Kaneko, Chikara
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p. 941 - 949
(2007/10/02)
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- Nitroethylene: A Stable, Clean, and Reactive Agent for Organic Synthesis
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Contrary to current belief, nitroethylene is a stable reagent and holds promise as a useful and reactive synthon.Nitroethylene can be prepared in 20-25-g lots, and standard, refrigerated solutions in common solvents provide a good and ready source of the reagent.The reagent purity can be easily monitored by titration against tetraphenylcyclopentadienone (tetracyclone) coupled with the isolation of the colorless crystalline adduct.With reactive substrates, nitroethylene reacts with greatest ease at low temperatures, leading to functionalized systems having potential for further elaboration.With systems that require heating, the limited stability of nitroethylene itself complicates the course of the reaction.Cyclopentadiene, 5-cyclopentadiene, 5-(methoxymethyl)cyclopentadiene, 5-(1,3-dithianyl)cyclopentadiene, 5-(trimethylsilyl)cyclopentadiene, and spiroheptadiene readily gave (4 + 2) adducts with nitroethylene, each possessing attraction as a synthetic intermediate.Adducts from furan and acetoxyfulvene undergo rearrangement via ? cleavage.The (4 + 2) adduct from 9-diazofluorene spontaneously extrudes nitrogen, leading to spironitrocyclopropane.Indole readily undergoes Michael addition to give 80percent 3-(nitroethyl)indole and 15percent of novel bis adduct.The 2,6 Michael adduct arises with 1-morpholinocyclohexene, and β-pinene undegoes an ene reaction with nitroethylene.Novel 2-nitroethyl phosphonates, useful in Wittig-Horner reactions, arise from nitroethylene and phosphites in tert-butyl alcohol.
- Ranganathan, Darshan,Rao, C.Bhushan,Ranganathan, Subramania,Mehrotra, Ashok K.,Iyengar, Radha
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p. 1185 - 1189
(2007/10/02)
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