Construction of an optically active 7-oxabicyclo[4.3.0]non-4-en-3-one skeleton from D-glucose, and its transformation to some pseudo-hexopyranoses.

スポンサーリンク

概要

• 論文の詳細を見る

• A versatile chiral compound, (1<I>R</I>,6<I>R</I>,8<I>R</I>,9<I>R</I>)-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]non-4-en-3-one (<B>6</B>), was efficiently synthesized from D-glucose. The synthesis featured an intramolecular aldol cyclization of 3-<I>C</I>-acetylmethyl-3-deoxy-1,2-<I>O</I>-isopropylidene-α-D-<I>ribo</I>-pentodialdo-1,4-furanose, which was readily derivatized from the known Wittig adducts of 1,2:5,6-di-<I>O</I>-isopropylidene-α-D-<I>ribo</I>-hexofuranos-3-ulose. The utility of this highly functionalized chiral synthon <B>6</B> was embodied by conversion to four optically active pseudosugars, these are pentaacetyl derivatives of pseudo-α-L-altropyranose, pseudo-β-D-glucopyranose, pseudo-2-amino-2-deoxy-β-L-altropyranose, and pseudo-2-amino-2-deoxy-α-D-glucopyranose (a derivative of pseudoglucosamine). The transformation of <B>6</B> to the pseudo sugars involved 1) a stereospecific epoxidation of the double bond in <B>6</B> providing (1<I>R</I>,4<I>S</I>,5<I>S</I>,6<I>S</I>,8<I>R</I>,9<I>R</I>)-4,5-epoxy-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]nonan-3-one (<B>8</B>), and 2) an exclusive diaxial ring opening of the β-epoxy alcohols, which were derived from <B>8</B>, providing (1<I>R</I>,3<I>R</I>,4<I>S</I>,5<I>S</I>,6<I>S</I>,8<I>R</I>,9<I>R</I>)-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]nonane-3,4,5-triol (<B>11</B>) or (1<I>R</I>,3<I>S</I>,4<I>S</I>,5<I>R</I>,6<I>S</I>,8<I>R</I>,9<I>R</I>)-4-azido-8,9-isopropylidenedioxy-7-oxabicyclo[4.3.0]nonane-3,5-diol. Treatment of (1<I>R</I>,2<I>S</I>,3<I>S</I>,4<I>S</I>,5<I>R</I>)-3,4,5-tris(benzyloxy)-2-hydroxycyclohexanecarbaldehyde, which was derived from <B>11</B>, with methanesulfonyl chloride, and successive sodium borohydride reduction provided (3<I>S</I>,4<I>S</I>,5<I>R</I>)-3,4,5-tris(benzyloxy)-1-cyclohexene-1-methanol (<B>19</B>). Hydroboration of <B>19</B> proceeded from the less hindered side stereoselectively.

• 公益社団法人 日本化学会の論文

著者

• Tadano Kin-ichi

  Department Of Applied Chemistry Faculty Of Science And Technology Keio University

• Suami Tetsuo

  Department of Applied Chemistry Faculty of Engineering Keio University

• Ueno Yoshihide

  Department of Applied Chemistry, Faculty of Science and Technology, Keio University

• Fukabori Chiyoko

  Department of Applied Chemistry, Faculty of Science and Technology, Keio University

• Hotta Yukinori

  Department of Applied Chemistry, Faculty of Science and Technology, Keio University

関連論文

• P-12 NATURAL PRODUCTS SYNTHESIS FEATURED BY SEQUENCIAL OLEFIN METATHESIS
• Total Syntheses of (+)-1893B and Its Three Diastereomers and Evaluation of Their Biological Activities
• Total Syntheses of Natural Pseurotins A, F_2, and Azaspirene
• PB166 SYNTHETIC STUDIES ON (+)-ASTELTOXIN, A NOVEL MYCOTOXIN ISOLATED FROM ASPERGILLUS STELLATUS : STEREOSELECTIVE SYNTHESIS OF THE BIS (TETRAHYDROFURAN) MOIETY (C-1 TO C-9)
• P-100 SYNTHETHIC STUDY OF SPICULOIC ACID A
• Synthesis of potential antineoplastic anthracenedione derivatives. I. Sugar derivatives.
• Synthesis of potential antineoplastic anthracenedione derivatives. II. 1,2-Dihydroxy derivatives.
• Nucleoside analogs. 4. Synthesis of 3'-amino-3'-deoxyadenosine analogs.
• Nucleoside analogs. 6. A synthesis of carbocyclic puromycin analogs.
• Nucleoside Analogs. II. A Synthesis of 9-Adenyl-deoxyinositols
• Synthesis on 1,4-diaminocyclitol antibiotics. IV. Synthesis of 7'-phenylfortimicin A and 7'-phenyl-6'-epifortimicin A.
• Synthetic approach toward antibiotic tunicamycins. II.
• Pseudo-sugars. VI. Synthesis of six isomers of 5-hydroxymethyl-1,2,3,4-cyclohexanetetrol (pseudo-hexopyranose) and their derivatives.
• Aminocyclitols. 36. Chlorination and dechlorination of aminocyclitol and inositol derivatives. Preparation of dideoxy- and trideoxystreptamines.
• Synthetic approach toward antibiotic ezomycins. II Synthesis of 5-amino-3,7-anhydro-5-deoxyoctofuranose-(1,4) derivatives.
• Total syntheses of (+)-altholactone[(+)-goniothalenol] and three stereocongeners and their cytotoxicity against several tumor cell lines.
• Chemical modification of neamine. 5. Preparation of amino-deoxyneamines.
• Synthesis of cytidine, uridine, and adenosine 5'-(2,6-diamino-2,6-dideoxy-.ALPHA.-D-glucopyranosyl diphosphates) (neosamine C-CDP, -UDP, and -ADP).
• Aminocyclitols. 34. Synthesis of inosadiamine-1,4 derivatives.
• Proton Magnetic Resonance Studies on Specifically Deuterated Sucrose Acetates
• Aminocyclitols. XXVIII. Bromination of Inosamines and Inosadiamines
• Synthesis of Planteose
• Synthesis of pseudo-.BETA.-DL-galactopyranose and pseudo-.ALPHA.-DL-altropyranose.
• Inositol Derivatives. IV. Synthesis of Anhydro Derivatives of 1,2-O-Cyclohexylidene-inositol
• Inositol Derivatives. V. Selective Benzoylation of 1,2-O-Cyclohexylidene-myo-inositol and Preparation of New O-p-Tolylsulfonyl-myo-inositols
• Synthetic studies on the validamycins. XII. Synthesis of optically active valienamine and validatol.
• Synthetic approach toward antibiotic tunicamycins.
• Synthesis of stachyose tetradecaacetate and an isomer.
• Synthesis of (2-chloroethyl)-nitrosourea derivatives of carbohydrate.
• Studies of tritylated pentoses and 6-deoxyhexoses. II. Trityl ethers of methyl .ALPHA.- and .BETA.-L-rhamnopyranoside and their derivatives.
• Claisen rearrangements of 5,6-dideoxy-1,2-o-isopropylidene-.ALPHA.-D-xylo- and .ALPHA.-D-ribo-hept-5-eno-1,4-furanoses with triethyl orthoacetate.
• Syntheses of optically active pentaacetates of pseudo-.BETA.-L-allopyranose and pseudo-.ALPHA.-D-mannopyranose.
• The synthesis of purpurosamine B derivatives.
• Synthesis on 1,4-diaminocyclitol antibiotics. II Synthesis of 7'-propylfortimicin A.
• Synthetic studies on the validamycins. IX. Synthesis of some racemic isomers of validoxylamine A.
• Pseudo-sugars. XIV. Synthesis of sweet-tasting pseudo-.BETA.-DL-fructopyranose.
• Synthetic studies on the validamycins. II. Synthesis of 1L-1-O-(.BETA.-D-glucopyranosyl)-(1,3,4/2,6)-4-amino-6-hydroxymethyl-1,2,3-cyclohexanetriol.
• Synthetic studies on the validamycins. III. Bromination of DL-tri-O-acetyl-(1,3/2)-4-methylene-5-cyclohexene-1,2,3-triol. Preparation of several branched-chain unsaturated cyclitols related to valienamine.
• Pseudo-sugars. 4. A facile synthesis of DL-validamine and its derivative.
• Pseudo-sugars. X. Synthesis of several branched-chain unsaturated cyclitols and their derivatives.
• Pseudo-sugars. VIII. Synthesis of DL-1-epivalidamine and related compounds.
• Synthesis and biological activities of 2-amino-2-deoxy- and 6-amino-6-deoxy-.ALPHA.-D-glucopyranosyl-2,5-dideoxystreptamines.
• Synthesis and epoxidation of trans-5,6-diacetoxy-1-benzoyloxymethyl-1,3-cyclohexadiene.
• Aminocyclitols. XXVI. A Synthesis of Aminocyclopentanetetrols
• Modification of aminocyclitol antibiotics. 6. Preparation of 5-deoxykanamycin B.
• Synthesis of Carbocydic Adenosine Analogs: 9-(2′,3′,4′,5′-Tetrahydroxycyclopentyl)adenines
• Construction of an optically active 7-oxabicyclo[4.3.0]non-4-en-3-one skeleton from D-glucose, and its transformation to some pseudo-hexopyranoses.
• Hydrazinolysis of Sugar Sulfonates
• A synthesis of (+)-cyclaradine, carbocyclic analogue of 9-.BETA.-D-arabinofuranosyladenine.
• Synthesis on 1,4-diaminocyclitol antibiotics. V Synthesis of 3'-enofortimicin D.
• Synthetic studies on the validamycins. I. Synthesis of .BETA.-D-glucopyranosylvalidamine: 1L-2-O-(.BETA.-D-Glucopyranosyl)-(1,3,4/2,6)-4-amino-6-hydroxymethyl-1,2,3-cyclohexanetriol.
• Inositol derivatives. 10. Isopropylidenation of 1,2-O-cyclohexylidene-myo-inositol derivatives and preparation of unaccessible blocked inositols.
• Selective p-Toluenesulfonylation of myo-Inositol Derivatives
• Synthesis of mono-O-tritylraffinoses and deca-O-acetylraffinoses.
• Pseudo-sugars. 3. Alternative synthesis of penta-N,O-acetyl-DL-validamine and its analogs.
• Aminocyclitols. XXVII. Preparation of Deoxyinosamines from vibo-Quercitol
• Aminocyclitols. XXIX. Synthesis of Inosadiamines via 1,3-Biimino-1,3-dideoxy-inositols
• Aminocyclitols. XXIV. Synthesis of Inosamines from Bromodeoxyinositols
• p-Toluenesulfonylation of 1,2-O-Cyclohexylidene-myo-inositol
• Pseudo-sugars. 5. Synthesis of DL-validatol and DL-deoxyvalidatol, and their epimers.
• Inositol Derivatives. VI. Convenient Synthesis of DL-profo-Quercitol from myo-Inositol
• Synthetic studies of the spirocyclic cyclohexene part of versipelostatin, a novel GRP78/Bip molecular chaperone downregulator

もっと見る 閉じる

スポンサーリンク