- A Fit-for-Purpose Synthesis of (R)-2-Methylazepane
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The preparation of new RSV inhibitors required an efficient synthesis of (R)-2-methylazepane ((R)-1) amenable to large-scale production to support preclinical studies. After consideration of different options, an efficient five-step synthesis relying on t
- Guizzetti, Sylvain,Michaut, Antoine,Federspiel, Guillaume,Eymard, Julien,Caron, Isabelle,Quatrevaux, Sabrina,Daras, Etienne,Jolly, Sandrine,Guillemont, Jér?me,Lan?ois, David
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p. 729 - 733
(2020/01/31)
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- BRIDGED TRICYCLIC CARBAMOYLPYRIDONE COMPOUNDS AND THEIR PHARMACEUTICAL USE
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Compounds for use in treating or preventing human immunodeficiency virus (HIV) infection are disclosed. The compounds have the following formula (I): including stereoisomers and pharmaceutically acceptable salts thereof, wherein R1, R2, L, W1, W2, X, Y, and Z are as defined herein. Methods associated with the preparation and use of such compounds, as well as pharmaceutical compositions comprising such compounds, are also disclosed.
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Paragraph 0409; 0415
(2020/10/20)
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- A Facile Direct Route to N-(Un)substituted Lactams by Cycloamination of Oxocarboxylic Acids without External Hydrogen
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Lactams are privileged in bioactive natural products and pharmaceutical agents and widely featured in functional materials. This study presents a novel versatile approach to the direct synthesis of lactams from oxocarboxylic acids without catalyst or external hydrogen. The method involves the in situ release of formic acid from formamides induced by water to facilitate efficient cycloamination. Water also suppresses the formation of byproducts. This unconventional pathway is elucidated by a combination of model experiments and density functional theory calculations, whereby cyclic imines (5-methyl-3,4-dihydro-2-pyrrolone and its tautomeric structures) are found to be favorable intermediates toward lactam formation, in contrast to the conventional approach encompassing cascade reductive amination and cyclization. This sustainable and simple protocol is broadly applicable for the efficient production of various N-unsubstituted and N-substituted lactams.
- Li, Hu,Wu, Hongguo,Zhang, Heng,Su, Yaqiong,Yang, Song,Hensen, Emiel J. M.
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p. 3778 - 3784
(2019/08/07)
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- Direct and Catalytic Amide Synthesis from Ketones via Transoximation and Beckmann Rearrangement under Mild Conditions
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The Br?nsted acid-catalyzed synthesis of secondary amides from ketones under mild conditions is described via transoximation and Beckmann rearrangement using O-protected oximes as more stable equivalents of explosive O-protected hydroxylamines. This methodology could be applied to highly rearrangement-selective amide synthesis from α-branched alkyl aryl ketones and performed on a 1-g scale. The presence of water is essential for this reaction, and its role was clarified by isotope-labeling experiments.
- Hyodo, Kengo,Hasegawa, Genna,Oishi, Naoki,Kuroda, Kazuma,Uchida, Kingo
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p. 13080 - 13087
(2018/11/02)
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- DISUBSTITUTED AZEPAN OREXIN RECEPTOR ANTAGONISTS
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The present invention is directed to disubstituted azepan and oxazepan amide compounds which are antagonists of orexin receptors, and which are useful in the treatment or prevention of neurological and psychiatric disorders and diseases in which orexin re
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Page/Page column 39
(2010/05/13)
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- Pushing radical cyclization from regioselective to regiospecific: Cyclization of amidyl radicals controlled by vinylic halogen substitution
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Efficient and regiospecific 6-exo, 7-endo, 7-exo, and even 8-endo amidyl radical cyclizations can be accomplished by the direct reactions of unsaturated N-H amides if they bear a vinylic halogen (Cl, Br, I) substituent. This remarkable halogen-substitution effect could be rationalized in terms of lone pair-lone pair electron repulsion between the N radical and the vinylic halogen atom, in addition to the well-known steric and radical-stabilizing effect.
- Hu, Tianshun,Shen, Meihua,Chen, Qian,Li, Chaozhong
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p. 2647 - 2650
(2007/10/03)
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- Silica sulfuric acid as a reusable catalyst for the conversion of ketones into amides by a Schmidt reaction under solvent-free conditions
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Silica sulfuric acid is a highly efficient reagent for the conversion of a variety of ketones into the corresponding amides by a Schmidt reaction under solvent-free conditions. Cyclic, aliphatic and aromatic ketones with electron-donating or withdrawing substituents may be converted easily in excellent yield. The major advantages of this method are: operational simplicity, the ready availability of the reagent, selectivity, general applicability, mild reaction conditions, short reaction times and high yields. The recovered catalyst could be used in new attempts without any purification.
- Eshghi, Hossein,Hassankhani, Asadollah,Mosaddegh, Elaheh
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p. 218 - 219
(2007/10/03)
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- P2O5/SiO2-catalyzed one-pot synthesis of amides from ketones via schmidt reaction under microwave irradiation in dry media
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A facile and efficient method for the preparation of amides from ketones by the Schmidt reaction is described for the first time using P 2 O 5 /SiO 2 and sodium azide under solvent-free microwave irradiation. Advantages of this procedure are selectivity, good yields, a simple operation, short reaction time, and solvent-free conditions. Copyright Taylor & Francis Group, LLC.
- Eshghi, Hossein,Hassankhani, Asadollah
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p. 2211 - 2216
(2007/10/03)
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- Indium trifluoromethanesulfonate (In(OTf)3)- A new catalyst for Beckmann rearrangement of ketoximes and facile dehydration of aldoximes
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Indium trifluoromethanesulfonate is found to be an effective catalyst for the facile dehydration of aldoximes to nitriles and Beckmann rearrangement of ketoximes to anilides in excellent yields.
- Barman, Dhiren C.,Gohain, Mukut,Prajapati, Dipak,Sandhu, Jagir S.
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p. 154 - 156
(2007/10/03)
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- Microwave induced bismuth trichloride catalysed Beckmann rearrangement of oximes
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A new and efficient method for the rearrangement of oximes 1 has been achieved by a simple reaction of a ketoximes with bismuth trichloride under microwave irradiation in the solid state.
- Thakur, Ashim J.,Boruah, Anima,Prajapati, Dipak,Sandhu, Jagir S.
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p. 2105 - 2111
(2007/10/03)
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- Dimethoxyethane as an alternative solvent for Schmidt reactions. Preparation of homochiral N-(5-oxazolyl)oxazolidinones from N-acetoacetyl derivatives of oxazolidinones
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Dimethoxyethane is an useful solvent for the Schmidt reaction of ketones and β-ketoesters with sodium azide and methanesulfonic acid to afford amides and amidoesters. This solvent is an alternative to the unsafe chlorinated solvents normally used. A β-diketone and several (4S)-N-(2-alkylacetoacetyl)-4-benzyloxazolidin-2-ones afford oxazoles under those conditions.
- Galvez, Nicanor,Moreno-Manas, Marcial,Sebastian, Rosa M.,Vallribera, Adelina
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p. 1609 - 1616
(2007/10/03)
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- STEREOSELECTIVE FORMAL SYNTHESIS OF (+/-)-MONOMORINE I FROM 6-METHYL-2-PIPERIDINONE
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The stereoselective formal synthesis of (+/-)-monomorine I from 6-methyl-2-piperidinone was achieved.A general method for the synthesis of ω-alkylated lactams is also described.
- Nagasaka, Tatsuo,Kato, Hiroki,Hayashi, Hideki,Shioda, Masako,Hikasa, Hiromi,Hamaguchi, Fumiko
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p. 561 - 566
(2007/10/02)
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- Clay Catalysed Facile Beckmann Rearrangement of Ketoximes
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Beckmann rearrangement is reported using montmorilonite KSF, an acidic clay.
- Meshram, H.M.
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p. 3253 - 3258
(2007/10/02)
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- SILICON-DIRECTED BECKMANN FRAGMENTATION
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The selective fragmentation reactions of β-trimethylsilylketoximes have been proved to proceed effectively with acid catalysts giving the corresponding nitriles.Cyclic silylketoximes gave unsaturated nitriles.The fragmentation in the Beckmann rearrangement is completely controlled and directed by a trimethylsilyl group to lead the regio- and stereo-specific formation of the double bond.The catalytic fragmentation proceeds with the combination of trimethylsilyl ketoxime acetates and trimethylsilyl trifluoromethanesulfonate giving nitriles in high yields.Excellent stereospecificity of the fragmentation based on the stereochemical outcome was discussed.Simple stereo-controlled synthetic approach to some insect pheromones is also described.
- Nishiyama, Hisao,Sakuta, Koji,Osaka, Noriyuki,Arai, Hiroyuki,Matsumoto, Makoto,Itoh, Kenji
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p. 2413 - 2426
(2007/10/02)
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- Nitrogen Bridgehead Compounds. 66. Bronchodilator Nitrogen Bridgehead Compounds with a Pyrimidinone Moiety
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New types of bronchodilator agents, bi- and tricyclic nitrogen bridgehead compounds with a pyrimidin-4(3H)-one ring, were synthesized and evaluated for bronchodilator activity against serotonin-, histamine-, and acetylcholine-induced spasms in the guinea pig Konzett-Roessler test.The structure-activity relationships are discussed.The effects of some bi- and tricyclic derivatives on the human bronchus were also investigated.The homologous tricyclic compounds 68 and 69 were tested on isolated guinea pig ileum and trachea, and the effects of compound 69 were investigated in pilocarpine-treated dogs.Azepinoquinazoline (69;CHINOIN-1289) was selected for further biochemical and clinical investigations.
- Hermecz, Istvan,Vasvari-Debreczy, Lelle,Horvath, Agnes,Balogh, Maria,Koekoesi, Jozsef,et al.
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p. 1543 - 1549
(2007/10/02)
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- Ruthenium Tetroxide Oxidation of N-Alkyllactams
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Ruthenium tetroxide (RuO4) oxidation of N-alkyllactams proceeded regioselectively depending on the size of lactam ring, except for the seven-membered ring.Four- and eight-membered N-methyl- and N-ethyllactams were oxidized at the exocyclic α-carbon adjacent to nitrogen to produce the N-acyllactams and NH-lactams, while five- and six-membered lactams underwent endocyclic oxidation to yield the cyclic imides.Oxidation of seven-membered lactams yielded a mixture of products arising from both exocyclic and endocyclic oxidations.These regioselectivities were confirmed in the oxidation of substrates having a tertiary carbon at the oxidation position.Keywords---oxidation; ruthenium tetroxide oxidation; regioselective oxidation; hydroxylation; imide synthesis; N-alkyllactam; N-acyllactams; imide; ruthenium tetroxide; two-phase method
- Yoshifuji, Shigeyuki,Arakawa, Yukimi,Nitta, Yoshihiro
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p. 357 - 363
(2007/10/02)
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- EFFECT OF TRIMETHYLSILYL GROUPS ON BECKMANN REARRANGEMENTS AND FRAGMENTATIONS
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Cyclic β-silyl ketones react with hydroxylamine-O-sulfonic acid in water to give as the major products olefinic nitriles resulting from silicon-directed Beckmann fragmentation reactions.
- Hudrlik, Paul F.,Waugh, Morris A.,Hudrlik, Anne M.
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- Novel Intramolecular Photorearrangement of Nitronate Anions
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The photochemistry of alkanenitronate anions is described.Irradiation of the alkanenitronate anions leads to hydroxamic acids by oxygen photorearrangement via ?-?* triplet excited states.The stoichiometry of reaction, anion structure and selectivity of migration, the nature of the excited state, the quantum yield of reaction, rehybridization on excitation, and the base dependency are discussed.From the results of a detailed structural study of 19 products it was found that this photorearrangement is a highly regio- and stereospecific reaction.
- Yamada, Kazutoshi,Tanaka, Seiji,Naruchi, Kiyoshi,Yamamoto, Makoto
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p. 5283 - 5289
(2007/10/02)
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