Synthetic studies of rifamycins. VIII. An improved practical synthesis of the ansa-chain compounds for the rifamycin W synthesis.
スポンサーリンク
概要
- 論文の詳細を見る
The improved practical synthesis of 6,8,10-tri-<I>O</I>-acetyl-3-<I>C</I>-(acetoxymethyl)-3,5,7,9,11-pentadeoxy-1,2-<I>O</I>-isopropylidene-5,7,9,11-tetra-<I>C</I>-methyl-L-<I>erythro</I>-D-<I>altro</I>-β-L-<I>talo</I>-dodecodialdofuranose-(1,4) 12-(diethyl acetal) (<B>3</B>), a useful synthetic segment for the rifamycin W ansa-chain, is described. The key intermediate, 3-<I>O</I>-benzyl-2,4,7-trideoxy-5,6-<I>O</I>-isopropylidene-2,4-di-<I>C</I>-methyl-<I>aldehydo</I>-D-<I>allo</I>-heptose (<B>22</B>), was synthesized in a 29.4% yield from methyl 4,6-<I>O</I>-benzylidene-3-deoxy-3-<I>C</I>-methyl-α-D-altropyranoside (<B>8</B>) in 15 steps. The coupling of <B>22</B> with the lithium reagent prepared from butyllithium and 3-<I>C</I>-(benzyloxymethyl)-3,5,6-trideoxy-5-iodo-1,2-<I>O</I>-isopropylidene-α-D-ribo-5-hexenofuranose afforded only the "Cram" product <B>24</B> in a 61% yield. The homogeneous hydrogenation of <B>24</B> with [RhCl(Ph<SUB>3</SUB>P)<SUB>3</SUB>] gave 8-<I>O</I>-benzyl-3-<I>C</I>-(benzyloxymethyl)-3,5,7,9,12-pentadeoxy-1,2:5,6-di-<I>O</I>-isopropylidene-5,7,9-tri-<I>C</I>-methyl-D-<I>erythro</I>-D-<I>altro</I>-L-<I>talo</I>-dodecofuranose-(1,4) (<B>25</B>) and its C-5 epimer in 95 and 3.8% yields respectively. 6,8-Di-<I>O</I>-benzyl-3-<I>C</I>-(benzyloxymethyl)-3,5,7,9-tetradeoxy-1,2-<I>O</I>-isopropylidene-5,7,9-tri-<I>C</I>-methyl-D-<I>altro</I>-β-L-<I>talo</I>-decodialdofuranose-(1,4), derived from <B>25</B> in a 91% yield, was subjected to coupling with 3,3-diethoxy-2-lithio-1-propene to afford about 1.7:1 excess of the "Cram" product (<B>30</B>, 59% yield). The conversion of <B>30</B> into <B>3</B> was accomplished by the sequence of reactions involving homogeneous hydrogenation, debenzylation, and acetylation in a 75% yield. The 24-step synthesis of <B>3</B> from <B>8</B> was achieved in a 7% overall yield.
- 公益社団法人 日本化学会の論文
著者
-
Nakata Masaya
Department Of Applied Chemistry Faculty Of Science And Technology Keio University
-
Toshima Kazunobu
Department Of Applied Chemistry Faculty Of Science And Technology Keio University
-
Kinoshita Mitsuhiro
Department of Applied Chemistry Engineering Faculty of Keio University
-
Kai Toshiyuki
Department of Applied Chemistry, Faculty of Science and Technology, Keio University
関連論文
- Preparation of Poly(β-malic acid)by Enzymatic Ring-Opening Polymerization of Benzyl β-Malolactonate
- P-122 CHEMICAL STUDIES ON THE SWEAT OF THE HIPPOPOTAMUS
- ILI-2 THE RED SWEAT OF THE HIPPOPOTAMUS(Isolation and Structure Elucidation of Natural Products)
- Synthetic Studies on Oilgomycins. Synthesis of the Oligomycin B Spiroketal and Polypropionate Portions
- Practical Synthesis of Four Stereoisomers of 6-(t-Butyldiphenylsiloxy)-3,5-dimethyl-1-(triphenylmethoxy)hexane-2,4-diol via Dithiane Coupling with Oxirane
- Synthetic Studies on Biscembranoids. Asymmetric Total Synthesis of the 14-Membered Diene Unit of Methyl Sarcophytoate^#
- Ally-C-Glycosidation of Glycals Mediated by 2,3-Dichloro-5,6-dicyano-p-benzoquinone (DDQ)
- Enzyme-catalyzed Ring-opening Polymerization of β-Butyrolactone Using PHB Depolymerase
- Synthesis and Properties of Polycarboxylate-type Green Surfactants with S- or N-Linkages
- Poly (Ricinoleic Acid) Based Novel Thermosetting Elastomer
- Synthesis and Properties of Biodegradable and Chemically Recyclable Cationic Surfactants Containing Carbonate Linkages
- Enzymatic Synthesis of Surface Active and Biodegradable Glucosaminide Fatty Acid Esters
- A Strategy for Increasing Molecular Weight of Polyester by Lipase-Catalyzed Polymerization
- ジおよびトリグリセリン脂肪酸エステルの酵素合成、海面活性、抗菌性および生分解性
- Biocatalytic One-step Synthesis of n-Octyl β-D-Xylotrioside and Xylobioside from Xylan and n-Octanol in Supercritical Carbon Dioxide
- Novel Direct Preparation of n - Butyl 2 - Amino - 2 - deoxy - β - D - glucopyranoside from Chitosan and n - Butanol Using Biocatalyst
- Enzymatic Preparation of Malate - Based Polycarboxylates Having Higher Molecular Weights by Copolymerization with Lactone
- n-アルキルキシロシド,キシロビオシド及びキシロトリオシドの界面活性,抗菌性及び生分解性
- Preparation of Novel Biodegradable Polyampholyte : Partially Dicarboxylated Chitosan
- Target-selective degradation of cancer-related proteins by novel photosensitizers for molecular-targeted photodynamic therapy
- Hydrolysis of Disaccharides by Metal Species in Neutral Homogeneous Solutions
- Enantioselective Production of (S)-3-Hydroxybutyric Acid, (S)-1,3-Butanediol and (R)-1,3-Butanediol Using Methanol Yeast
- セルラーゼとβ-グルコシダーゼの組み合わせによるセルロースと1-オクタノールからの1-オクチルβ-D-グルコシドのワンポット合成
- Environmentally Benign and Stereoselective Construction of 2-Deoxy and 2,6-Dideoxy-β-glycosidic Linkages Employing 2-Deoxy and 2,6-Dideoxyglcosyl Phosphites and Montmorillonite K-10
- Novel Enzyme-Catalyzed Ring-Opening Polymerization of Glycidol
- Lipase-Catalyzed Reaction of Molecularly Pure Linear and Cyclic Poly(3-hydroxybutanoate)s : Evidence of Cyclic Polymer Formation
- Room-Temperature Metallation of 2-Substituted 1,3-Dithiane Derivatives and Subsequent Coupling with 2,3-Disubstituted Oxiranes
- The Suitable Timing of Contrast Medium before Three-Dimensional Rotational Angiography of the Left Atrium (LA) for the Patients with Atrial Fibrillation (AF)
- Radiation Exposure Associated with Preoperative Multidetector Computed Tomography of Pulmonary Vein Isolation
- A Novel Analysis Program Using 64-Multidetector Row Computed Tomography for the Evaluation of Left Ventricular Mechanical Dyssynchrony
- Studies on Antibiotics and Related Substances. X. Syntheses of Some Unsaturated Ketocarboxylic Acids, Anti-tumor Substances
- Synthetic studies of amphotericin B. III. An enantiospecific synthesis of the C-1-C-19 segment of the amphotericin B aglycon.
- Total synthesis of aminoglycoside antibiotics, apramycin and saccharocin (KA-5685).
- Synthetic approach to 2,3,5-triamino-2,3,5-trideoxy-D-arabonic acid derivatives from 3,4,6-triazido-3,4,6-trideoxy-1,2-O-isopropylidene-.ALPHA.-D-glucopyranose.
- Creation of Novel Biofunctional Molecules for Target-Selective Photodegradation of Proteins and Carbohydrates : A Synthetic and Chemical Biological Study for the Post-Genome Era
- Enantiodivergent total syntheses of nanaomycins and their enantiomers, kalafungins.
- Syntheses of (3S, 4R, 15S)-4,15-Dimethyl-1,5-dioxa-3-(3′-formamidosalicylamido)-cyclopentadecane-2,6-dione and Its (15R)-Epimer, New Antimycin Analogs
- Total synthesis of a macrocyclic lactone antibiotic A26771B and its isomers using carbohydrates.
- A novel synthesis of a branched-chain amino sugar, methyl 2-amino-2,3-dideoxy-3-C-formyl-.ALPHA.-D-xylofuranoside-3'R,5-hemiacetal.
- Synthetic studies of rifamycins. III. The partial synthesis of rifamycin ansa-chain compounds from their degradation products.
- Synthetic studies of rifamycins. IV. The synthesis of rifamycin ansa-chain compound using carbohydrate.
- Studies on Aminosugars. XXIX. Syntheses of Nucleosides of 3-Amino-3-deoxy-3-C-hydroxymethyl-β-D-ribofuranose
- Total synthesis of elaiophylin (azalomycin B).
- Synthetic studies of rifamycins. II. Syntheses of methyl 2,4,6,7-tetradeoxy-4-C-methyl-3-O-METHYL-.ALPHA.-L-arabino-heptopyranosid-6-ulose and its derivatives utilizable in the construction of the rifamycin ansa chain portion.
- Synthetic studies of rifamycins. VIII. An improved practical synthesis of the ansa-chain compounds for the rifamycin W synthesis.
- Synthesis of Cyclic α-Amino Acids. IV. Syntheses of Adenine Nucleosides of 3-Amino-3-C-carboxy-3-deoxy-D-ribofuranose and 3-Amino-3-C-carboxy-3-deoxy-D-ribopyranose
- An enantiospecific synthesis of the C-21-C-37 segment of the aglycon of amphotericin B.
- Synthesis of (3S, 4S)- and (3S, 4R)-4-Amino-3-hydroxy-6-methylheptanoic Acid, and Their N-(Acetyl-L-valyl-L-valyl) Derivatives
- Stereospecific Synthesis of Natural (+)Blastmycinone and Its Three (2R)-Diastereomers
- Synthetic studies of erythromycins. IV. Total synthesis of erythronolide A.
- Total Syntheses of Antimycin A3 and Its Diastereomer