3-O-benzyl 1,2-O-isopropylidene-5,6-O-sulfuryl-α-D-glucofuranose | 158946-12-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-O-benzyl 1,2-O-isopropylidene-5,6-O-sulfuryl-α-D-glucofuranose
• 英文别名: 3-O-Benzyl-1,2-O-isopropylidene-α-D-glucofuranose-5,6-O-sulfate；(4R)-4-[(3aR,5S,6S,6aR)-2,2-dimethyl-6-phenylmethoxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-1,3,2-dioxathiolane 2,2-dioxide
• CAS: 158946-12-4
• 化学式: C₁₆H₂₀O₈S
• 分子量: 372.396
• InChiKey: FXIYZIRWYNWWME-UXXRCYHCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  97.9
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  3-O-benzyl 1,2-O-isopropylidene-5,6-O-sulfuryl-α-D-glucofuranose 在 palladium on activated charcoal sodium azide 、 硫酸 、 氢气 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 25.0~50.0 ℃ 、101.33 kPa 条件下， 反应 12.0h， 生成 6-amino-6-deoxy-1,2-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  Completely regioselective synthesis of 5- and 6- amino and fluoro-hexofuranoses via cyclic sulphates

  摘要：

  The nucleophilic opening of new and previously described 5,6- and 3,5-glucohexofuranose cyclic sulphates is a regioselective and efficient way to prepare 6- and 5-azido(amino)- and 6- and 5-fluoro-aldofuranose derivatives (D-gluco and L-ido configurations). (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01529-9
• 作为产物：
  描述：

  (1R)-1-((3aR,6S,6aR)-6-(benzyloxy)-2,2-dimethyltetrahydrofuro(2,3-d)(1,3)dioxol-5-yl)ethane-1,2-diol 在 ruthenium trichloride 、 sodium periodate 、 thionyl diimidazole 作用下， 生成 3-O-benzyl 1,2-O-isopropylidene-5,6-O-sulfuryl-α-D-glucofuranose
  参考文献：
  名称：

  Synthesis of 3-trialkylsilyl pyrazoles from β-oxo acylsilanes

  摘要：

  The synthesis of beta -oxo acylsilanes via cyclic sulfates is described and applied to carbohydrates. These compounds are used for the synthesis of new silylated pyrazoles linked to a carbohydrate moiety by the addition of hydrazines. The regiochemistry of the reaction was determined by NMR analyses (H-1/C-13 and H-1/N-15 correlations). (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01724-x

文献信息

• Regioselective Synthesis of 6-Alkynyl-6-Deoxy and Pseudo-C-Disaccharides Derivatives of Mannofuranose via a 5,6-Cyclic Sulfate
  作者：Thierry Gourlain、Anne Wadouachi、Daniel Beaupère

  DOI：10.1055/s-1999-3389

  日期：1999.2

  C-6 opening of a 5,6-cyclic sulfate derivative of mannofuranoside 1 with acetylenic anion generated from oct-1-yne or phenylethyne gave corresponding 6-alkynyl-6-deoxy derivatives 2 and 3 respectively. The reaction of 5,6-cyclic sulfate 1 with lithium acetylide derived from monosaccharide led to pseudo-C-disaccharide 5. A one-pot procedure was achieved using lithium acetylide in THF/HMPA, to prepare symmetric pseudo-C-disaccharide 7. This method, used with a 5,6-cyclic sulfate derivative of glucofuranose 11 with the acetylide anion derived from mannofuranose 9, gave the corresponding nonsymmetric pseudo-C-disaccharide 13.

  C-6开环反应：利用从辛-1-炔或苯乙炔生成的炔基负离子，打开甘露呋喃糖苷1的5,6-环硫酸酯衍生物，分别得到相应的6-炔基-6-脱氧衍生物2和3。5,6-环硫酸酯1与源自单糖的锂炔化物反应，形成伪C-二糖5。通过在THF/HMPA中使用锂炔化物的一锅法程序，制备了对称伪C-二糖7。该方法应用于葡萄呋喃糖11的5,6-环硫酸酯衍生物，与源自甘露呋喃糖9的炔化负离子反应，得到相应的非对称伪C-二糖13。
• Synthesis of 3,6-anhydro sugars from cyclic sulfites and sulfates and their applications in the preparation of bicyclonucleoside analogues of ddC and ddA
  作者：M.Pineda Molas、M.Isabel Matheu、Sergio Castillón、Joaquín Isac-García、Fernando Hernández-Mateo、Francisco G. Calvo-Flores、Francisco Santoyo-González

  DOI：10.1016/s0040-4020(99)00911-4

  日期：1999.12

  Cyclic sulfates 21–23 and sulfite 27 derived from glucofuranose lead to the 3,6-anhydrosugar 28 in excellent yields when treated with sodium sulfite or in basic media. When treated with sodium sulfite, the 3-deoxy derivative 24 fails to give the intramolecular cyclization which leads to the anhydrosugars. Instead it gives the disulfonate derivative 26. 28 was used as starting material to prepare bicyclonucleosides

  当用亚硫酸钠或在碱性介质中处理时，衍生自葡糖呋喃糖的环状硫酸盐21 – 23和亚硫酸盐27以极高的产率生成3,6-脱水糖28。当用亚硫酸钠处理时，3-脱氧衍生物24不能产生分子内环化作用，从而导致脱水糖。相反，它给出二磺酸盐衍生物26。使用28作为起始原料制备双环核苷43和46，它们是抗HIV药物ddC和ddA的类似物。
• Synthesis of sugar episulfides and olefins from via-diols via cyclic sulfates
  作者：Francisco Santoyo-González、Francisco García-Calvo-Flores、Pilar García-Mendoza、Fernando Hernandez-Mateo、Joaquín Isac-García、Ma Dolores Pérez-Alvarez

  DOI：10.1039/c39950000461

  日期：——

  Cyclic sulfates of vic-diols are transformed in one-pot into sugar episulfides by treatment with potassium thioacetate or thiourea followed by reaction with sodium methoxide; reaction of these cyclic sulfates with potassium selenocyanate followed by treatment with sodium borohydride allows the synthesis of sugar olefins.

  的环硫酸酯VIC -diols通过与硫代乙酸钾或治疗转化在一锅转化为糖环硫化物的硫脲，接着用甲醇钠反应; 这些环状硫酸盐与硒氰酸钾反应，然后用硼氢化钠处理，可以合成糖烯烃。
• Synthesis of Carba Analogues of Deoxy-4-C-(hydroxymethyl)hexopyranoses, Intermediates in the Synthesis of Carbocyclic Nucleosides
  作者：Hubert Hřebabecký、Antonín Holý

  DOI：10.1135/cccc20010785

  日期：——

  3-O-Benzyl-1,2-O-isopropylidene-α-D-glucofuranose-5,6-O-sulfate (1) was treated with sodium salt of dimethyl malonate to obtain, after hydrolysis, methyl 5-(3-O-benzyl-1,2-O-isopropylidene-α-D-erythrofuranos-4-yl)-2-oxotetrahydrofuran-3-carboxylate (3) which was converted to the mixture of methyl (2S,3R,4R)- (7) and (2R,3R,4R)-2-(acetyloxy)-3-(benzyloxy)-4-(formyloxy)-7-oxo-6-oxabicyclo[3.2.1]octane-1-carboxylate (8). The compound 7 was reduced with lithium aluminium hydride to give (1R,2R,3R,4S)-3-(benzyloxy)-5,5-bis(hydroxymethyl)cyclohexane-1,2,4-triol (9) which was transformed to (1R,2S,4R)-5,5-bis(hydroxymethyl)cyclohexane-1,2,4-triol (14). Treatment of sodium salt of diethyl malonate with 3-O-benzyl-5,6-dideoxy-6-iodo-1,2-O-isopropylidene-α-D-xylo-hexofuranose (19) gave diethyl (3-O-benzyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-xylo-hexofuranos-6-yl)malonate (20) which was converted to (1R,3R)-4,4-bis(hydroxymethyl)cyclohexane-1,3-diol (28) by a similar procedure to that used for 14.

  3-O-苄基-1,2-O-异丙基亚-D-葡萄糖呋喃糖-5,6-O-硫酸酯（1）经过与二甲基丙二酸钠盐反应，水解后得到甲基5-(3-O-苄基-1,2-O-异丙基亚-D-赤霉糖-4-基)-2-氧代四氢呋喃-3-羧酸甲酯（3），再转化为甲基(2S,3R,4R)-(7)和(2R,3R,4R)-2-(乙酰氧基)-3-(苄氧基)-4-(甲酰氧基)-7-氧代6-氧杂双环[3.2.1]辛烷-1-羧酸甲酯（8）的混合物。化合物7经过锂铝氢化还原得到(1R,2R,3R,4S)-3-(苄氧基)-5,5-双(羟甲基)环己烷-1,2,4-三醇（9），进而转化为(1R,2S,4R)-5,5-双(羟甲基)环己烷-1,2,4-三醇（14）。将3-O-苄基-5,6-二脱氧-6-碘-1,2-O-异丙基亚-D-木糖-呋喃糖（19）与二乙酸二乙酯钠盐反应，得到二乙酸(3-O-苄基-5,6-二脱氧-1,2-O-异丙基亚-D-木糖-呋喃糖-6-基)酯（20），再经类似于14的过程转化为(1R,3R)-4,4-双(羟甲基)环己烷-1,3-二醇（28）。
• Applications of Cyclic Sulfates of <i>vic</i>-Diols:  Synthesis of Episulfides, Olefins, and Thio Sugars
  作者：Francisco G. Calvo-Flores、Pilar García-Mendoza、Fernando Hernández-Mateo、Joaquín Isac-García、Francisco Santoyo-González

  DOI：10.1021/jo962066b

  日期：1997.6.13

  A new efficient and expeditious one-pot synthesis of thiiranes and olefins from cyclic sulfates of vic-diols is described. Opening of cyclic sulfates with potassium thioacetate or potassium thiocyanate followed by treatment with sodium methoxide led to episulfides. Olefins were obtained when potassium selenocyanate was used as nucleophile, and the obtained monoesters were treated with sodium borohydride. This method was applied to acyclic polyols derived from chiral glycerine, 1,2-isopropylidenehexofuranoses with different subtituents at C-3, and dimethyl acetals derived from pentoses and hexoses. The methodology is highly versatile, and its applicability has been demonstrated by the synthesis of different 4- and 5-thiosugars by opening of the thiirane ring with sodium acetate or lithium aluminum hydride. Reduction with lithium aluminum hydride of the thiocyanate sulfate potassium salt obtained by the opening of cyclic sulfate with KSCN allowed the direct synthesis of 5-deoxy-4-thio- and 6-deoxy-5-thiosugars. Cyclic thiosugars with the sulfur atom in the ring are obtained by acidic hydrolysis of the 5-thiol derivatives of 1,2-O-isopropylidenehexofuranoses and 4-thiopentose dimethyl acetals. Using this method, an efficient synthesis of 5-thio-L-fucose as well as the synthesis of 2,5-dideoxy-4-thiofuranose is described.