- Rhodium-Catalyzed Cyclization of O,ω-Unsaturated Alkoxyamines: Formation of Oxygen-Containing Heterocycles
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O,ω-Unsaturated N-tosyl alkoxyamines undergo unexpected RhIII-catalyzed intramolecular cyclization by oxyamination to produce oxygen-containing heterocycles. Mechanistic studies show that an aziridine intermediate seems to be responsible for the formation of the heterocycles, possibly via a RhV species.
- Escudero, Julien,Bellosta, Véronique,Cossy, Janine
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supporting information
p. 574 - 578
(2018/02/21)
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- NOVEL OXADIAZOLE DERIVATIVE AND PHARMACEUTICAL CONTAINING SAME
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An amyloid fibril formation inhibitor comprising a compound represented by the following general formulae (I) to (III): wherein Q is -C(=O)-; X is -C(=O)-, -NH-C(=O)-; Y is -(CH2)m-; Z is -(CH2)n-; R1
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Paragraph 0189
(2018/02/28)
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- Synthesis of Panal Terpenoid Core
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Panal is a natural bicyclic cadalane-type sesquiterpenoid with an unusual combination of stereocenters. It was isolated in 1988 as an alleged biosynthetic precursor of luciferin (a light-emitting molecule) in a bioluminescent fungus Panellus stipticus. Herein we present the first approach to the synthesis of the terpenoid skeleton of panal, which includes construction of five stereocenters, one of which is easily epimerizable. The key steps in the synthetic approach presented are high-pressure Diels-Alder reaction disobeying the ‘endo rule’, Barbier reductive allylation, and cyclization of trans-decalin ring via ring-closing metathesis.
- Baranov, Mikhail S.,Kaskova, Zinaida M.,Gritсenko, Roman,Postikova, Svetlana G.,Ivashkin, Pavel E.,Kislukhin, Alexander A.,Moskvin, Dmitrii I.,Mineev, Konstantin S.,Arseniev, Alexander S.,Labas, Yulii A.,Yampolsky, Ilia V.
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p. 583 - 588
(2017/03/11)
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- ANTIBACTERIAL AGENTS
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Antibacterial compounds of formula (I) are provided, as well as stereoisomers and pharmaceutically acceptable salts thereof; pharmaceutical compositions comprising such compounds; methods of treating bacterial infections by the administration of such compounds; and processes for the preparation of such compounds.
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- METHODS AND COMPOSITIONS FOR THE SYNTHESIS OF MULTIMERIZING AGENTS
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The invention features methods and compositions for the synthesis of multimerizing agents.
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Page/Page column 16
(2012/08/08)
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- Development of a practical and scalable synthesis of (R)- and (S)-3-amino-2-[(benzyloxy)methyl]propan-1-ol monohydrochloride: A useful C-4 Chiral Building Block
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The development of a practical and scalable synthesis of a C-4 chiral amine building block (R)-1·HCl and (S)-1·HCl is described. This important chiral intermediate (R)-1·HCl is efficiently synthesized from the commercially available, inexpensive, and simple 2-(hydroxymethyl)-1,3- propanediol (31) using lipase-catalyzed enantioselective hydrolysis as a key reaction. Development resulted in a telescoped process that was operated successfully and reproducibly in a pilot-plant-scale synthesis, and 22 kg of chiral amine (R)-1·HCl was prepared in the first scale-up synthesis. This synthetic method is also useful for preparation of the important chiral building block (S)-1·HCl, which is the enantiomer of (R)-1·HCl.
- Yoshida, Shinya,Obitsu, Kazuyoshi,Hayashi, Yasumasa,Shibazaki, Mitsuyoshi,Kimura, Takenori,Takahashi, Takumi,Asano, Toru,Kubota, Hirokazu,Mukuta, Takashi
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p. 1527 - 1537
(2013/02/23)
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- 3,5-Disubstituted pyranone analogues of highly antifungally active furanones: Conversion of biological effect from antifungal to cytostatic
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A series of 3-aryl-5-acyloxymethyl-5,6-dihydro-2H-pyran-2-ones, related to highly antifungally active butenolides, was synthesized via cyclization of substituted δ-hydroxy acids as the key step, and evaluated for their in vitro antifungal activity and cytostatic activity. While the extension of the furanone ring to pyranone led to a complete loss of the antifungal effect, some of the compounds displayed promising effect against several cell lines, including the resistant colorectal carcinoma cells.
- Schiller, Radan,Tichotová, Lucie,Pavlík, Jan,Buchta, Vladimír,Melichar, Bohuslav,Votruba, Ivan,Kune?, Ji?í,?pulák, Marcel,Pour, Milan
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scheme or table
p. 7358 - 7360
(2011/01/12)
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- Pyrazole glucokinase activators
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Disclosed herein are pyrazole glucokinase activators of the formula (I) useful for the treatment of metabolic diseases and disorders, preferably diabetes mellitus.
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Page/Page column 81
(2008/06/13)
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- Bifunctional acyclic nucleoside phosphonates: 2. Symmetrical 2-{[bis(phosphono)methoxy]methyl}ethyl derivatives of purines and pyrimidines
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Novel bisphosphonate alkylating agent, tetraisopropyl (2-[(mesyloxy)methyl] propane-1,3-diyl]bis(oxymethylene)bisphosphonate 19, was synthesized from diethyl 2,2-bis-(hydroxymethyl)malonate. Decarbethoxylation of the diethyl 2,2-dimethyl-1,3-dioxane-5,5-dicarboxylate was followed by chloromethylation of 2-[(benzyloxy)methyl]propane-1,3-diol and Arbuzov reaction with triisopropyl phosphite. Bisphosphonate building block 19 was used in the alkylation of various nucleobases (2-amino-6-chloropurine, adenine, 2-amino-6-(cyclopropyl) aminopurine, cytosine, uracil and 4-methoxy-5-methylpyrimidin-2(1H)-one). N 9-Substituted purines and N1-substituted pyrimidines were converted to appropriate free bisphosphonic acids. No antiviral or cytostatic activity was detected.
- Vrbkova, Silvie,Dracinsky, Martin,Holy, Antonin
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p. 965 - 983
(2008/09/20)
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- Synthetic studies on azadirachtin: An efficient asymmetric synthesis of the highly functionalized tricyclic decalin part of azadirachtin
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The detailed examination of intramolecular Diels-Alder reactions of several structurally related trienes led to construction of the desired tricyclic decalin moiety of azadirachtin with the α-hydroxyl groups at C1 and C3 as well as the oxygenated substituent at C8 in the naturally occurring form in good yields.
- Yamamoto,Ishihara,Kanoh,Murai
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p. 1894 - 1906
(2007/10/03)
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- Synthetic studies on azadirachtin: Construction of the highly functionalized decalin moiety of azadirachtin
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Construction of the left segment of azadirachtin in naturally occurring enantiomer is described. The key reaction is an intramolecular Diels-Alder reaction, which was performed under thermal conditions to afford the highly functionalized decalin compounds selectively.
- Ishihara, Jun,Yamamoto, Yuuko,Kanoh, Naoki,Murai, Akio
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p. 4387 - 4390
(2007/10/03)
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- Synthetic studies on spiroketal natural products. IV. A stereoselective synthesis of (3S,5S,6R,9R,R(S))-3-benzyloxymethyl-9-hydroxymethyl-5-(p-tolyl)sulfin yl-1,7-dioxaspiro[5.5]undecane, a key intermediate for talaromycins
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A dioxaspiro compound (4), a common intermediate for the synthesis of talaromycin A (1) and (-)-talaromycin B (2), was synthesized by two routes utilizing two kinds of asymmetric recognition of prochiral 1,3-diols controlled by sulfinyl chirality, that is, firstly by acid promoted diastereoselective C-O bond fission of the bicyclic acetal (7) to give the dihydropyran derivative (6), which has an S-hydroxymethyl group at the C3-position (7 → 6), and secondly by diastereoselective intramolecular Michael addition of the diol (5), in which the three chiral centers at C5, C6, C9 were constructed in one step (5 → 4).
- Iwata,Maezaki,Hattori,Fujita,Moritani,Takemoto,Tanaka,Imanishi
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p. 339 - 345
(2007/10/02)
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- SYNTHESIS OF 5,5'-DIHYDROXYLEUCINE AND 4-FLUORO-5,5'-DIHYDROXYLEUCINE, THE REDUCTION PRODUCTS OF 4-CARBOXYGLUTAMIC AND 4-CARBOXY-4-FLUOROGLUTAMIC ACIDS
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Schemes for the synthesis of 5,5'-dihydroxyleucine 3 and its 4-fluoro analog 7 involving the condensation of a suitable 'aminoacid moiety' with 2,2-dimethyl-5-iodomethyl-1,3-dioxane 15D or its fluoro analog 27A were tested.The anion of the ethyl N-diphenylmethylene-glycinate 25 gave better yields of 3 than the classical anion of diethyl acetamidomalonate.This strategy could not be successfully applied to the synthesis of 7, which could be prepared by reduction of a suitably protected 4-fluoro-4-carboxyglutamate with BMS.
- Dubois, Joelle,Foures, Christine,Bory, Sonia,Falcou, Serge,Gaudry, Michel,Marquet, Andree
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p. 1001 - 1012
(2007/10/02)
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- Synthesis and Evaluation of Phospholipid Analogues as Inhibitors of Cobra Venom Phospholipase A2
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Analogues of phospholipids that contain fluoro ketone, ketone, and alcohol replacements for the ester at the 2-position of the glycerol backbone have been prepared and analyzed as inhibitors of phospholipase A2 from Naja naja naja venom.Phospholipid analogues were studied that contain two alkyl chains as well as single chain compounds that lack carbon-1 of the glycerol backbone and the attached acyl unit.Compounds that contain both long and medium length alkyl chains were studied.All of the potential inhibitors were tested in a well-defined mixed micelle system in which both the substrates and the inhibitors have been incorporated into Triton X-100 micelles.Surprisingly, the best inhibitors studied were the single chain fluoro ketones despite the fact that the enzyme has a strong preference for two-chain lipids.The most potent compound was found to have a dissociation constant some 600-3000-fold lower than the Michaelis constant for dipalmitoyl phosphatidylcholine substrate. 19F NMR studies of the fluoro ketone phospholipid analogues in micelles show that whereas the single chain compounds are partially in the hydrated-ketone form, the two-chain compounds are less than 0.1percent hydrated.In every case studied, potent inhibition of phospholipase A2 was observed only with those compounds that are significantly hydrated in the micelle, and it is suggested that the hydrated fluoro ketone containing phospholipid analogues are the species responsible for the inhibition.In addition, the single chain fluoro ketones were better inhibitors than single and double chain alcohol and ketone analogues.Previous studies have been show that the cobra venom enzyme is activated by choline-containing lipids, and evidence is presented for the binding of the hydrated fluoro ketone inhibitors selectively to the activated enzyme.
- Yuan, Wei,Berman, Richard J.,Gelb, Michael H.
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p. 8071 - 8081
(2007/10/02)
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- An Approach to Pseudomonic Acids from Acetylenic Precursors: Synthesis of 2-(Hydroxymethyl)-3-butyn-1-ol
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The acetonide of 2-(hydroxymethyl)-3-butyn-1-ol (17) was prepared from bis(hydroxymethyl)malonate (11) or from 1,3-dihydroxypropanone (22).Alternative routes to 17 involving the intermediacy of highly unstable alkynal 21 or the corresponding acetate were unsuccessful.Condensation of the anion of 17 with aldehyde 30 followed by semihydrogenation and deprotection afforded keto triol 33, which cyclized stereoselectively to dihydropyran 34.Osmylation and functional group manipulation afforded 40 and 42, precursors to pseudomonic acid C (1).
- Bates, Hans Aaron,Farina, James,Tong, Michael
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p. 2637 - 2641
(2007/10/02)
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- 2-Hydroxymethyl-1,3-propanediol preparation
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2-Hydroxymethyl-1,3-propanediol trinitrate, processes for its preparation, and compounds related thereto are disclosed. The final product is useful as a plasticizer of relatively low volatility in double based propellant compositions and as a liquid explosive.
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