5,6-Didesoxy-5,6-epithio-1,2-O-isopropyliden-α-L-idofuranose | 16749-41-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,6-Didesoxy-5,6-epithio-1,2-O-isopropyliden-α-L-idofuranose
• 英文别名: (3aR,5S,6R,6aR)-2,2-dimethyl-5-[(2R)-thiiran-2-yl]-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-ol
• CAS: 16749-41-0
• 化学式: C₉H₁₄O₄S
• 分子量: 218.274
• InChiKey: ZBWORIXQRDHVRT-TVNFTVLESA-N

物化性质

• 沸点：
  360.0±42.0 °C(Predicted)
• 密度：
  1.382±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  73.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5,6-Didesoxy-5,6-epithio-1,2-O-isopropyliden-α-L-idofuranose 在 lithium aluminium tetrahydride 、 sodium methylate 、 溶剂黄146 作用下， 以 四氢呋喃 、 吡啶 为溶剂， 反应 3.0h， 生成 (2S,3R,4S,5S,6S)-6-methylthiane-2,3,4,5-tetrol
  参考文献：
  名称：

  Applications of Cyclic Sulfates of vic-Diols:  Synthesis of Episulfides, Olefins, and Thio Sugars

  摘要：

  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.

  DOI：

  10.1021/jo962066b
• 作为产物：
  描述：

  1,2-o-异亚丙基-alpha-d-呋喃葡萄糖-3-乙酸酯 在 ruthenium trichloride 、 sodium periodate 、 氯化亚砜 、 sodium methylate 、 三乙胺 作用下， 以 甲醇 、 四氯化碳 、 二氯甲烷 、 水 、 丙酮 、 乙腈 为溶剂， 反应 3.0h， 生成 5,6-Didesoxy-5,6-epithio-1,2-O-isopropyliden-α-L-idofuranose
  参考文献：
  名称：

  Applications of Cyclic Sulfates of vic-Diols:  Synthesis of Episulfides, Olefins, and Thio Sugars

  摘要：

  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.

  DOI：

  10.1021/jo962066b

文献信息

• Reaction of sugar epoxides with phosphorothioic acids, evidence of the pentacoordinate phosphorus intermediate in the reaction of 5,6-anhydro-1,2-0-is0propylidene-α-d-glucofuranose with phosphorothioic acids
  作者：Wiesława Kudelska、Maria Michalska

  DOI：10.1016/s0040-4020(01)87463-9

  日期：1986.1

  The reaction of sugar epoxides with organic monothioacids of phosphorus provides a convenient procedure for synthesizing sugar thiophosphates and mercaptosugar phosphates. Based on detailed analysis of intermediates and factors influencing the reactivity of phosphorus monothioacids with sugar epoxides the reaction acheme is proposed involving pentacoordinate intermediate which undergoes endo or/and

  糖环氧化物与磷的有机一硫代酸的反应为合成糖硫代磷酸酯和巯基糖磷酸酯提供了便利的程序。基于中间体的详细分析和影响单硫代酸磷与糖环氧化物反应性的因素，提出了反应戊二烯，涉及经过内部或/和环外消除的五配位中间体。我们发现5，6-脱水-1,2-0-异亚丙基-α-D-呋喃呋喃糖7与硫代磷酸8a和8b的反应产生了三种平衡的产物：硫代磷酸盐9a和9b，氧杂环丁烷-膦酸酯11a和11b以及巯基磷酸盐10a和10b。在更剧烈的条件下，磷酸盐10a和10b可以不可逆地转化为过硫化物12和磷酸13a和13b，分别地 很显然，化合物10和11都可以由相同的五配位中间体形成，并且实验证据对此提供了有力的支持。
• Utilization of Sugars in Organic Synthesis. Part XXXI. Solvolytic Behaviors of O-Benzoyl, Cyclic O,O-Thionocarbonate, and O,S-Thiolcarbonate Groups in 3-0-Benzoyl-1,2-0-isopropylidene-.ALPHA.-D-glucofuranose Derivatives.
  作者：Yoshisuke TSUDA、Kenji SHIBAYAMA

  DOI：10.1248/cpb.44.1476

  日期：——

  O-Benzoyl, cyclic thionocarbonate, and thiolcarbonate groups in 5, 6-O-thiono-, 5, 6-O, S-thio-l, and 5, 6-S, O-thiolcarbonates of 3-O-benzoyl-1, 2-O-isopropylidene-α-D-glucofuranoses behaved differently on solvolysis under alkaline conditions. Generally, the 3-O-benzoyl group was the most vulnerable to NaOH in water or MeOH, while thionocarmonate and thiolcarbonate groups were more reactive than the O-benzoyl group toward methanolysis with NaOMe. In particular, methanolysis of the 5, 6-S, O-thiolcarbonate with NaOMe gave a thiirane derivative very rapidly.

  5, 6-O-thiono-、5, 6-O、S-thio-1和5, 6-S、O-thiolcarbonates的3-O-benzoyl-1, 2-O-isopropylidene-α-D-glucofuranoses中的O-benzoyl、环硫碳酸酯和硫碳酸酯基团在碱性条件下的溶解性表现不同。一般来说，3-O-benzoyl基团在水或甲醇中的NaOH作用下最易受损，而硫碳酸酯和硫碳酸盐基团对NaOMe发生甲醇解时比O-benzoyl基团更具反应性。特别是，5, 6-S、O-thiolcarbonate与NaOMe的甲醇解反应迅速生成了一种硫杂环烷烃衍生物。
• 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。
• O,O-dialkylphosphoro-thioic and -dithioic acids as functionalising reagents of monosaccharides: synthesis of 6-(dialkoxyphosphinylthio)-α-D-glucofuranoses, and a new route to 5,6-episulphides
  作者：Wieslawa Kudelska、Maria Michalska

  DOI：10.1016/s0008-6215(00)85362-8

  日期：1980.8
• 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.