- Enantioselective synthesis of (S)-2-amino-3-phosphonopropionic acid, (S)-AP-3, and (R)-2-amino-4-phosphonobutanoic acid, (R)-AP-4, via diastereoselective azidation of (4R,5R)-trans-N-[(diethoxyphosphoryl)propionyl]- and (4R,5R)-trans-N-[(diethoxyphosphoryl)butanoyl]hexahydrobenzoxazolidin-2-one
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N-Acylation of readily available, enantiopure oxazolidinone (4R,5R)-1b with (diethoxyphosphoryl)propionyl chloride and (diethoxyphosphoryl)butanoyl chloride affords de title substrates (4R,5R)-2 and (4R,5R)-7, respectively, which are azidated with high diastereoselectivity by means of the reaction between their sodium enolates (4R,5R)-2-Na and (4R,5R)-7-Na with trisyl azide. Removal of the chiral auxiliary from azidated products (4R,5R,2′S)-3 and (4R,5R,2′R)-8 followed by hydrogenation and hydrolysis of the resulting carboxylic acids (S)-4 and (R)-9 gave the pharmacologically relevant aminophosphonic acids (S)-AP-3 and (R)-AP-4 in good yield.
- Reyes-Rangel, Gloria,Mara?ón, Virginia,Avila-Ortiz, C. Gabriela,Anaya de Parrodi, Cecilia,Quintero, Leticia,Juaristi, Eusebio
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Read Online
- OPTICALLY-ACTIVE 2-AMINO-PHOSPHONOALKANE ACID, OPTICALLY-ACTIVE 2-AMINOPHOSPHONOALKANE ACID SALT, AND HYDRATES OF THESE
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A novel compound has pharmacological activities comparable to those of Nahlsgen and is storable excellently stably. The compound can be produced by a method according to the present invention for producing an optically active 2-amino-phosphonoalkanoic acid salt. In the method, a starting material DL-2-amino-phosphonoalkanoic acid represented by Formula (1) or a hydrate thereof is reacted with an optically active basic compound other than an optically active lysine, to give a diastereomeric salt mixture including a first salt (including a hydrate salt) between a D-2-amino-phosphonoalkanoic acid represented by Formula (1-1) and the optically active basic compound, and a second salt (including a hydrate salt) between an L-2-amino-phosphonoalkanoic acid represented by Formula (1-2) and the optically active basic compound. The diastereomeric salt mixture is fractionally crystallized to isolate one of the first and second diastereomeric salts.
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Paragraph 0120-0139
(2020/05/14)
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- Involucrin gene expression promoter
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PROBLEM TO BE SOLVED: To provide an involucrin gene expression promoter that has high effect of promoting involucrin gene expression, and is applied to the skin, to quickly increase involucrin concentrations, and markedly improving the barrier function. SOLUTION: An involucrin gene expression promoter contains at least one selected from a compound represented by the following formula (1) [where R1 and R2 are the same or different to represent a hydrogen atom, or a substituent. n is an integer of 1 or greater], a salt thereof, and their hydrates as an active ingredient. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPO&INPIT
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Paragraph 0084; 0095
(2019/03/28)
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- A novel asymmetric synthesis of S-(+)-2-amino-4-phosphonobutanoic acid
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A novel asymmetric synthetic route to S(+)-2-amino-4-phosphonobutanoic acid through the cyclic condensation of ethyl-4-diethyoxyphosphonyl-2-oxo-butanoate with L-erythro-(+)-1,2-diphenyl-2-hydroxyethylamine, followed by reduction and hydrolysis is describ
- Jiao,Chen,Hu
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p. 1179 - 1186
(2007/10/02)
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- Asymmetric Syntheses via Heterocyclic Intermediates, XXXI.- Asymmetric Synthesis of Various Non-Proteinogenic Amino Acid Methyl Esters (Functionalized in the Carbon Chain) and Amino Acids by the Bislactim Ether Method
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The lithiated bislactim ethers 5, 10, 12, and 23 were alkylated with a variety of alkylating agents 6 to give the alkylated bislactim ethers 7, 11, 13, and 24 with a high degree of asymmetric induction (up to 99percent).Upon hydrolysis these furnished the optically active amino acid methyl esters of type 8, 14, or 25.Some of these amino acid esters were further hydrolyzed to yield the amino acids.
- Schoellkopf, Ulrich,Busse, Ulrich,Lonsky, Ralph,Hinrichs, Rolf
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p. 2150 - 2163
(2007/10/02)
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- PREPARATION D'ACIDES AMINOCARBOXY-ALKYLPHOSPHONIQUES OPTIQUEMENT ACTIFS
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In aqueous solution ω-formylalkylphosphonates in the presence of hydrogen cyanide and (S) (-) α-methylbenzylamine give optically active aminonitriles with an enantiomeric excess of 50percent.Phosphonic aminonitriles are submitted to acid hydrolysis, then esterified and debenzylated without any epimerization.The separation is performed either with the acid or with the ester.All the operations are monitored by NMR (1H, 13C, 31P) and whenever possible, by GC.
- Villanueva, J. M.,Collignon, N.,Guy, A.,Savignac, Ph.
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p. 1299 - 1306
(2007/10/02)
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