- Studies toward gymnodimine: development of a single-pot Hua reaction for the synthesis of highly hindered cyclic imines.
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[structure: see text]. In studies directed toward gymnodimine and related marine toxins, a single-pot variation of the Hua cyclic imine synthesis has been developed. The reaction involves generation of N-trimethylsilyl lactams in situ followed by alkyllithium addition leading directly to cyclic imines. Importantly, this reaction proceeds efficiently with highly hindered alpha,alpha-dialkyl lactams, provided 1,2-dimethoxyethane (DME) is used as solvent, leading to stable cyclic imines. Overall, this transformation allows a one-pot coupling of an alkyliodide and a lactam to give a cyclic imine.
- Ahn,Cardenas,Yang,Romo
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- Synthesis of Spirocyclic Imines: Key Pharmacophores in the Shellfish Toxins Spirolides and Gymnodimine
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The efficient synthesis of several spirocyclic imines of similar structure to that present in the shellfish toxins, the spirolides and gymnodimine, is described. The key steps involved double α-alkylation of simple lactam starting materials, Grubbs' ring closing metathesis of the resultant bis-alkylated lactams and LiEt3BH reduction of the TEOC protected lactams to imines.
- Trzoss, Michael,Brimble, Margaret A.
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- Lactamomethylsilanes – Synthesis, Structures, and Reactivity towards CO2 and Phenylisocyanate
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Lactamomethylsilanes of γ-butyrolactam, δ-valerolactam, ε-caprolactam, and 1-isoindolinone (phthalimidine) with up to three methyl moieties were synthesized according to the chemical formula MexSiLac(4–x) (x = 0, 1, 2, and 3). Using the lactams as starting materials four synthetic routes were tested: salt elimination, transsilylation, transamination, and metallation of the lactames followed by reaction with methylchlorosilanes. All products were analyzed by NMR (1H, 13C and 29Si) and RAMAN spectroscopy. Selected solid products were crystallized and the molecular structure was determined by single-crystal X-ray diffraction. The reactivity of the lactamomethylsilanes towards phenylisocyanate and CO2 was studied.
- Herbig, Marcus,B?hme, Uwe,Kroke, Edwin
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- Stereoselective electrochemical synthesis of silyl enol ethers using a sacrificial magnesium anode
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The 2-pyrrolidone magnesium salt electrogenerated in an undivided cell fitted with a sacrificial magnesium anode allowed the stereoselective synthesis of Z-silyl enol ethers upon deprotonation of enolizable ketones in the presence of a complexing agent. Keywords: Silyl enol ethers; Stereoselective synthesis; Electrogenerated bases; Sacrificial magnesium anode
- Bonafoux, Dominique,Bordeau, Michel,Biran, Claude,Dunogues, Jacques
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- A double alkylation - Ring closing metathesis approach to spiroimines
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As part of a programme directed towards the synthesis of the marine toxins, the spirolides and gymnodimine, a convenient synthesis of the key bicyclic spiroimine ring systems has been developed. The method involves double alkylation of a simple lactam, Grubbs ring closing metathesis of the resultant dialkylated lactam then reduction of the lactam to an imine.
- Brimble, Margaret A.,Trzoss, Michael
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- Preparation method of phosphate or phosphite and secondary battery. (by machine translation)
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The preparation method of the phosphate or phosphite ester disclosed by the invention comprises, the following steps: of: reacting inorganic phosphate or inorganic phosphite 3) with a phosphoric acid ester as shown in a formula (shown in the 1) formula); and preparing 2) the phosphate ester or the. phosphite. ester according to the invention as shown in the invention . (by machine translation)
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Paragraph 0075-0076
(2019/12/25)
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- Strong influence of intramolecular Si?O proximity on reactivity: Systematic molecular structure, solvolysis, and mechanistic study of cyclic N-trimethylsilyl carboxamide derivatives
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A comparative alcoholysis study of N-silylated derivatives of simple heterocyclic carboxamides (lactams, imides, ureas) is presented. The second-order rate constant values span a range as wide as three orders of magnitude. On the basis of DFT calculations, a good correlation between reactivity and the Si?O distance was found within each family of compounds. The viability of two different reaction pathways was evaluated using a detailed computational mechanistic study of the methanolysis of cyclic urea homologues. Peculiarities in the single-crystal X-ray diffraction structures of the trimethylsilyl and trimethylsiloxy phthalimides are also discussed.
- Szalay, Roland,Harmat, Veronika,E?ri, János,Pongor, Gábor
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supporting information
p. 2186 - 2192
(2017/05/16)
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- Highly effective asymmetric hydrogenation of cyclic N -alkyl imines with chiral cationic Ru-MsDPEN catalysts
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A range of cyclic N-alkyl imines were efficiently hydrogenated by using a chiral cationic Ru(η6-cymene)(MsDPEN)(BArF) complex (MsDPEN = N-(methanesulfonyl)-1,2-diphenylethylenediamine) in high yields and up to 98% ee. A one-pot synthesis of chiral 2-phenylpyrrolidine via reductive amination was also developed.
- Chen, Fei,Ding, Ziyuan,Qin, Jie,Wang, Tianli,He, Yanmei,Fan, Qing-Hua
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supporting information; experimental part
p. 4348 - 4351
(2011/10/13)
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- COMPOUNDS FOR TREATING DISORDERS MEDIATED BY METABOTROPIC GLUTAMATE RECEPTOR 5, AND METHODS OF USE THEREOF
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Provided herein are compounds and methods of synthesis thereof. The compounds set forth herein are useful for the treatment, prevention, and/or management of various disorders, such as neurological disorders, neurodegenerative disorders, neuropsychiatric disorders, disorders of cognition, learning or memory, gastrointestinal disorders, lower urinary tract disorder, and cancer. Compounds set forth herein modulate the activity of metabotropic glutamate receptor 5 (mGluR5) in the central nervous system or the periphery. Pharmaceutical formulations containing the compounds and their methods of use are also provided herein.
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Page/Page column 140
(2011/07/07)
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- Palladium-catalysed enantioselective α-hydroxylation of β-ketoesters
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Highly enantioselective α-hydroxylation of cyclic and acyclic 1,3-ketoesters can be achieved with up to 98% ee using a dicationic palladium(ii) catalyst and dimethyldioxirane as oxidant.
- Smith, Alexander M.R.,Billen, Denis,Hii, King Kuok
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supporting information; experimental part
p. 3925 - 3927
(2010/01/06)
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- Synthesis, conformational characteristics and anti-influenza virus A activity of some 2-adamantylsubstituted azacycles
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The broad-spectrum antiviral activity of 2-(2-adamantyl)piperidines 11, 13a,b, and 15, 3-(2-adamantyl)pyrrolidines 27, 21a-g and 2-(2-adamantylmethyl)piperidines 30, 32a-c, and 35a-d was examined. Several compounds in the new series were potent against influenza A H3N2 virus. When 1-aminoethyl pharmacophore group of 2-rimantadine 4 (2-isomer of rimantadine) is included into a saturated nitrogen heterocycle, see compound 11, potency was retained. The diamine derivatives 21e-g and particularly 35a-c possessing three pharmocophoric groups, that is, the adamantyl and the two amine groups, exhibited high potency. The new compounds did not afford specific activity at non-toxic concentrations against any of the other viruses tested. According to NMR spectroscopy and molecular mechanics calculations it is striking that the parent structures 11 and 27 adopt a fixed trans conformation around C2{single bond}C2′ bond. In the parent amines, which proved to be active compounds, the distance between nitrogen and adamantyl pharmacophoric groups was different; N{single bond}C2′ distance is 3.7, 3.8 A for 27, 30 and 2.5 A for 11 suggesting that M2 receptor site can accommodate different in size and orientation lipophilic cages.
- Setaki, Despina,Tataridis, Dimitris,Stamatiou, George,Kolocouris, Antonios,Foscolos, George B.,Fytas, George,Kolocouris, Nicolas,Padalko, Elizaveta,Neyts, Johan,Clercq, Erik De
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p. 248 - 273
(2008/02/07)
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- Synthesis of partially deuterated N-nitrosamines - New standards in tobacco-smoke analysis
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N-Nitrosamines of tobacco alkaloids contribute to the cause of tobacco related cancers and, therefore, they are important analytes. Herein the preparation of four partially deuterated N-nitrosamines from simple, commercially available, deuterated educts is described, which can serve as useful standards in tobacco-smoke analysis. Springer-Verlag 2004.
- Gaertner, Peter,Bica, Katharina,Einzinger, Christian
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p. 549 - 555
(2007/10/03)
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- HYDROXAMIC ACID DERIVATIVES FOR USE WITH THE TREATMENT OF DISEASES RELATED TO CONNECTIVE TISSUE DEGRADATION
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The present invention provides novel hydroxamic acid derivatives represented by the compound of formula I I or pharmaceutical acceptable salts thereof, wherein the compounds of the present invention inhibit various enzymes from the matrix metalloproteinase family, including collagenase, stromelysin, and gelatinase, and hence are useful for the treatment of matrix metallo endoproteinase diseases such as osteoarthrits, rheumatoid arthritis, septic arthritis, osteopenias such as osteoporosis, tumor metastasis (invasion and growth), periodontitis, gingivitis, corneal ulceration, dermal ulceration, gastric ulceration, and other diseases related to connective tissue degradation.
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- Novel 3-(2-adamantyl)pyrrolidines with potent activity against influenza A virus - Identification of aminoadamantane derivatives bearing two pharmacophoric amine groups
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The 3-(2-adamantyl)pyrrolidines 8a-g, 14 were synthesized and evaluated for activity against influenza A virus. The parent N-H compound 14 was several times more active than amantadine against H2N2 and H3N2 influenza A virus. The combined use of NMR spectroscopy and computational chemistry showed that the conformation around the pyrrolidine-adamantyl carbon-carbon bond is trans and the pyrrolidine heterocycle has an envelope conformation with C-2 out of the plane of the other ring atoms. N-Dialkylaminoethyl substitution of compound 14 resulted in the potent diamine analogues 8e,f,g. Interestingly, their lactam amine precursors were also active. Compounds 8e,f,g are the first adamantane derivatives, bearing two amine groups, reported to be active against influenza A virus.
- Stamatiou, George,Kolocouris, Antonios,Kolocouris, Nicolas,Fytas, George,Foscolos, George B,Neyts, Johan,De Clercq, Erik
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p. 2137 - 2142
(2007/10/03)
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- HYDROXAMIC ACID DERIVATIVES USEFUL FOR THE TREATMENT OF DISEASES RELATED TO CONNECTIVE TISSUE DEGRADATION
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The present invention provides novel hydroxamic acid derivatives represented by the compound of formula I STR1 or pharmaceutical acceptable salts thereof, wherein the compounds of the present invention inhibit various enzymes from the matrix metalloproteinase family, including collagenase, stromelysin, and gelatinase, and hence are useful for the treatment of matrix metallo endoproteinase diseases such as osteoarthrits, rheumatoid arthritis, septic arthritis, osteopenias such as osteoporosis, tumor metastasis (invasion and growth), periodontitis, gingivitis, corneal ulceration, dermal ulceration, gastric ulceration, and other diseases related to connective tissue degradation.
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- Synthesis and antiviral activity evaluation of some new aminoadamantane derivatives. 2
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The synthesis of some new aminoadamantane derivatives is described. The new compounds were evaluated against a wide range of viruses [influenza A H1N1, influenza A H2N2, influenza A H3N2, influenza B, parainfluenza 3, herpes simplex virus type 1 (HSV-1) and type 2 (HSV-2), thymidine kinase- deficient (TK-) HSV-1, vaccinia, vesicular stomatitis, polio 1, Coxsackie B4, Sindbis, Semliki forest, Reo 1, varicella-zoster virus (VZV), TK- VZV, human cytomegalovirus (HCMV), and human immunodeficiency virus type 1 (HIV- 1) and type 2 (HIV-2)]. Some of them proved markedly active against the influenza A H2N2 (compounds 4a,b, 5a, 6a, and 7a), H3N2 (compounds 5a, 6a, and 7a), and H1N1 (compounds 4b,c and 6d). Since compounds 5a, 6a, and 7a, amantadine, and rimantadine showed the same comparative pattern of potency against influenza strains H2N2, H3N2, and B, it may postulated that they act according to a similar mechanism, with regard to their 'amine' effect, on the M2 ion channel of influenza A (H1N1, H2N2, or H3N2). In general, no significant activity was noted with any of the new compounds against any of the other viruses tested, making their activity against influenza virus more specific and striking. Borderline activity was noted with some of the compounds (4b,c, 5a-c, and 8a) against HIV-1.
- Kolocouris, Nicolas,Kolocouris, Antonios,Foscolos, George B.,Fytas, George,Neyts, Johan,Padalko, Elisabeth,Balzarini, Jan,Snoeck, Robert,Andrei, Graciela,De Clercq, Erik
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p. 3307 - 3318
(2007/10/03)
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- N-Phosphorylated lactams 2. Reversible phosphorylation of silyllactams
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The phosphorylation of N-trimethylsilyllactams by phosphorus(III) acid chlorides results in corresponding N-phosphinolactams in high yields. The derivatives thus obtained have been used in the synthesis of N-phosphoryl- and N-thiophosphoryllactams. The reversibility of the reaction of phosphinolactams has been established. - Keywords: N-trimethylsilyllactams; reversible phosphorylation; N-phosphoryllactams, synthesis.
- Ouryupin, A. B.,Rakhov, L. A.,Kolesova, V. A.,Petrovskii, P. V.,Mastryukova, T. A.,Kabachnik, M. L.
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p. 2157 - 2162
(2007/10/03)
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- N-Phosphorylated lactams 2. Reversible phosphorylation of silyllactams
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The phosphorylation of N-trimethylsilyllactams by phosphorus(III) acid chlorides results in corresponding N-phosphinolactams in high yields.The derivatives thus obtained have been used in the synthesis of N-phosphoryl- and N-thiophosphoryllactams.The reversibility of the reaction of phosphinolactams has been established. - Keywords: N-trimethylsilyllactams; reversible phosphorylation; N-phosphorylactams synthesis.
- Ouryupin, A. B.,Rakhov, I. A.,Kolesova, V. A.,Petrovskii, P. V.,Mastryukova, T. A.,Kabachnik, M. I.
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p. 2157 - 2156
(2007/10/03)
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- SYNTHESIS OF N-(SILATRANYLMETHYL)-SUBSTITUTED LACTAMS AND CARBOXYLIC ACID AMIDES
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The general approach proposed for the synthesis of N-silatranylmethyl derivatives of lactams and carboxylic acid amides is based on the silyl variant of the akylation reaction.The treatment of N-trimethylsilyl-substituted lactams and carboxylic acid amides yielded N-trialkoxysilylmethyl lactam and amide derivatives.These were converted into the corresponding silatranes by the usual procedure (treating with triethanolamine in the presence of KOH).
- Kramarova, V.P.,Shipov, A.G.,Baukov, Yu.I.
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p. 2113 - 2119
(2007/10/02)
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- A MILD AND FACILE ROUTE TO ω-AMINO ESTERS
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Lactim ethers are conveniently prepared from the corresponding lactam.The salt prepared by protonation with HCl or HBF4 is hydrolyzed in neutral water at ambient temperatures to give good yields of the ω-amino ester.
- Menezes, Royce,Smith, Michael B.
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p. 1625 - 1636
(2007/10/02)
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- Pyrrolidin-2-ones and medicaments containing them
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The invention relates to pyrrolidinones of the general formula: STR1 in which: R1 represents hydrogen or alkyl R2 represents alkyl, phenyl or trimethylsilyl. R3 represents 2-thienyl or a phenyl possibly substituted once or twice with halogen, methyl, methoxy or a trifluoromethyl group. It relates also to a process for the production of these compounds and to the pharmaceutical compositions containing them.
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