General synthesis of homo-C-nucleosides.
スポンサーリンク
概要
- 論文の詳細を見る
Lithium aluminium hydride reduction of methyl (2,3-<I>O</I>-isopropylidene-5-<I>O</I>-trityl-β-D-ribofuranosyl) acetate gives 2-(2,3-<I>O</I>-isopropylidene-5-<I>O</I>-trityl-β-D-ribofuranosyl)ethanol. Subsequent tosylation, displacement by cyanide ion, nitrile hydrolysis, and diazomethane methylation afford methyl 3-(2,3-<I>O</I>-isopropylidene-5-<I>O</I>-trityl-β-D-ribofuranosyl)propionate. The base-promoted formylation followed by methylation with methyl iodide forms methyl 2-[(2,3-<I>O</I>-isopropylidene-5-<I>O</I>-trityl-β-D-ribofuranosyl)methyl]-3-methoxyacrylate. Base-catalyzed condensation of the methoxyacrylate and urea followed by deprotection produces 5-[(β-D-ribofuranosyl)methyl]uracil. In a like manner, condensation of the methoxyacrylate with thiourea or guanidine gives, after deblocking, 5-[(β-D-ribofuranosyl)methyl]-2-thiouracil and 5-[(β-D-ribofuranosyl)methyl]isocytosine, respectively. Ozonolysis of the methoxyacrylate yields methyl 3-(2,3-<I>O</I>-isopropylidene-5-<I>O</I>-trityl-β-D-ribofuranosyl)pyruvate, which undergoes condensation with carbamoylmethylenetriphenylphosphorane to furnish a mixture of methyl 2-[(2,3-<I>O</I>-isopropylidene-5-<I>O</I>-trityl-β-D-ribofuranosyl)methyl]fumaramate and 2-[(2,3-<I>O</I>-isopropylidene-5-<I>O</I>-trityl-β-D-ribofuranosyl)methyl]maleimide. Deprotection of the latter leads to 2-[(β-D-ribofuranosyl)methyl]maleimide. Condensation of the keto ester with ethyl hydrazinoacetate followed by cyclization affords 3-[(2,3,<I>O</I>-isopropylidene-5-<I>O</I>-trityl-β-D-ribofuranosyl)methyl]-5-methoxycarbonyl-4-hydroxypyrazole. Ammonolysis of the methyl ester and deprotection furnishes 3-[(β-D-ribofuranosyl) methyl]-5-carbamoyl-4-hydroxypyrazole.
- 公益社団法人 日本化学会の論文
著者
-
Noyori Ryoji
Department Of Chemistry And Molecular Chirality Research Unit Nagoya University
-
Sato Tsuneo
Department of Chemistry, Nagoya University
関連論文
- An Improved Method for the Synthesis of Allylic gem-Diacetates from α,β-Unsaturated Aldehydes Catalyzed by Lithium Tetrafluoroborate
- A Facile Procedure for Acetalization of Aldehydes and Ketones Catalyzed by Cerium(III) Trifluoromethanesulfonate
- Hyperconjugative Electron-Delocalization Mechanism Controlling the Conformational Preference of Fluoroacetaldehyde and Methyl Fluoroacetate
- Molecular Design of Prostaglandin Probes in Brain Research: High, Specific Binding to a Novel Prostacyclin Receptor in the Central Nervous System
- 1,4-Addition of Diorganozincs to α,β-Unsaturated Ketones Catalyzed by a Copper(I)-Sulfonamide Combined System
- A Practical Method for Alcohol Oxidation with Aqueous Hydrogen Peroxide under Organic Solvent- and Halide-Free Conditions
- Advancing Organic Synthesis
- A Halide-Free Method for Olefin Epoxidation with 30% Hydrogen Peroxide^#
- Conformational Study on 2-Acyl-1-alkylidene-1,2,3,4-tetrahydroisoquinolines
- Stereoseletive Organic Synthesis via Dynamic Kinetic Resolution
- Distribution and Genus/Species Composition of Histamine-Decomposing Bacteria during Storage of Common Mackerel
- INFLUENCES OF ALKALINE IONIZED WATER ON MILK ELECTROLYTE CONCENTRATIONS IN MATERNAL RATS
- ニホンザルの慢性上部消化管疾患における胃運動の機能低下
- The photochemical reaction of iron pentacarbonyl and 1,3-butadiene-1,1,4,4-d4. The lack of secondary isotope effects.
- Trimethylsilyl triflate induced reaction of humulene 6,7-epoxide. Cyclization to 5-hydroxy-4,8,11,11-tetramethyltricyclo(6.3.0.02,4)undec-9-ene.
- The Stereoselective Reduction of Tropinone to Tropine
- A stereocontrolled total synthesis of C-nucleosides.
- The Baeyer-Villiger oxidation of 8-oxabicyclo(3.2.1)octan-3-ones. Substituent effects on the regioselectivity.
- Synthesis of 3-carbamoyl-4-[(.BETA.-D-ribofuranosyl)methyl]pyrazole, a pyrazole homo-C-nucleoside.
- Nickel(0) catalyzed (2+2) cross-addition of bicyclo(2.2.1)heptene derivatives with electron-deficient olefins.
- Stereocontrolled general synthesis of pyrimidine C-nucleosides having branched-chain sugar moieties.
- Three-component coupling synthesis of prostaglandins: The aldol route.
- The Role of Nucleophilic Solvents in the Acid-Catalyzed Cyclization of a Cross-Conjugated Cycloalkadienone
- Photo-induced Polar Addition of Protic Solvents to Cycloalkenones. Evidence for the Ground-state trans Isomers as Chemically-reactive Intermediates
- Synthesis of 3(2H)-furanones by the iron carbonyl-promoted cyclocoupling reaction of .ALPHA.,.ALPHA.'-dibromo ketones and carboxamides. A conventient route to muscarines.
- Direct observation of dienol intermediates in photochemical deconjugation of an .ALPHA.,.BETA.-uusaturated ketone. Photoisomerization of 1-acetylcyclooctene.
- A cationic (3,4) sigmatropic rearrangement.
- The use of zinc/silver couple in the cyclocoupling reaction of polybromo ketones and furan.
- Ring opening of oxiranes by trimethylsilyl trifluoromethanesulfonate.
- A molecular orbital study of silylated carbenes.
- An easy preparation of triphenylmethyl carboxylates.
- General synthesis of homo-C-nucleosides.