methyl 2,3-O-isopropylidene-5,6-O-sulfuryl-α-D-mannofuranoside | 127244-81-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3-O-isopropylidene-5,6-O-sulfuryl-α-D-mannofuranoside
• 英文别名: (4R)-4-[(3aS,4S,6S,6aS)-4-methoxy-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-6-yl]-1,3,2-dioxathiolane 2,2-dioxide
• CAS: 127244-81-9
• 化学式: C₁₀H₁₆O₈S
• 分子量: 296.298
• InChiKey: BNZFABKYMLFCKC-DFTQBPQZSA-N

物化性质

• 沸点：
  409.0±45.0 °C(predicted)
• 密度：
  1.49±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  methyl 2,3-O-isopropylidene-5,6-O-sulfuryl-α-D-mannofuranoside 在 咪唑 、 六甲基磷酰三胺 、 正丁基锂 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 N,N-二甲基甲酰胺 、 xylene 为溶剂， 反应 15.0h， 生成 6,7,8-trideoxy-3-O-benzyl-1,2-O-isopropylidene-8-(methyl 5-O-tert-butyldiphenylsilyl-6-deoxy-2,3-O-isopropylidene-α-D-manno-furanosid-6-yl)-α-D-gluco-oct-7-ynofuranose
  参考文献：
  名称：

  Regioselective Synthesis of 6-Alkynyl-6-Deoxy and Pseudo-C-Disaccharides Derivatives of Mannofuranose via a 5,6-Cyclic Sulfate

  摘要：

  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。

  DOI：

  10.1055/s-1999-3389
• 作为产物：
  描述：

  methyl 2,3-O-isopropylidene-α-D-mannofuranoside 在 ruthenium trichloride 吡啶 、 sodium periodate 、 氯化亚砜 作用下， 以 二氯甲烷 、 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 1.0h， 生成 methyl 2,3-O-isopropylidene-5,6-O-sulfuryl-α-D-mannofuranoside
  参考文献：
  名称：

  环状硫酸盐在6-脱氧-d-甘露聚糖-吡喃糖衍生物合成中的应用

  摘要：

  摘要从2,3-O-异亚丙基-α-d-甘露吡喃糖苷4,6-硫酸甲酯或2,3-O-异亚丙基-α-d-甲基开始，分五步制备6-脱氧-d-甘露聚糖-七吡喃糖。 5，6-硫酸甘露呋喃糖苷。使用糖基供体乙基2,3,4,7-四-O-苯甲酰基-6-脱氧-1-硫代-α，β-d-甘露聚糖-七吡喃糖苷合成甲基4-O-（6-脱氧-α -d-甘露聚糖-七吡喃糖基）-β-d-吡喃半乳糖苷。

  DOI：

  10.1016/0008-6215(92)84105-2

文献信息

• Application of cyclic sulfates in the synthesis of 6-deoxy-d-manno-heptopyranose derivatives
  作者：Pieter A.M. van der Klein、Jacques H. van Boom

  DOI：10.1016/0008-6215(92)84105-2

  日期：1992.2

  6-Deoxy- d -manno-heptopyranose was prepared in five steps starting from methyl 2,3-O-isopropylidene-α- d -mannopyranoside 4,6-sulfate or methyl 2,3-O-isopropylidene-α- d -mannofuranoside 5,6-sulfate. The glycosyl donor ethyl 2,3,4,7-tetra-O-benzoyl-6-deoxyl-1-thio-α,β- d -manno-heptopyranoside was used to synthesise methyl 4-O-(6-deoxy-α- d -manno-heptopyranosyl)-β- d -galactopyranoside.

  摘要从2,3-O-异亚丙基-α-d-甘露吡喃糖苷4,6-硫酸甲酯或2,3-O-异亚丙基-α-d-甲基开始，分五步制备6-脱氧-d-甘露聚糖-七吡喃糖。 5，6-硫酸甘露呋喃糖苷。使用糖基供体乙基2,3,4,7-四-O-苯甲酰基-6-脱氧-1-硫代-α，β-d-甘露聚糖-七吡喃糖苷合成甲基4-O-（6-脱氧-α -d-甘露聚糖-七吡喃糖基）-β-d-吡喃半乳糖苷。
• A new 6-C-alkylation from an alkyl mannofuranoside 5,6-cyclic sulfate
  作者：Thierry Gourlain、Anne Wadouachi、Daniel Beaupère

  DOI：10.1016/s0008-6215(99)00275-x

  日期：2000.1

  Methyl 6-C-alkyl-6-deoxy-alpha-D-mannofuranoside derivatives have been synthesized from methyl 2,3-O-isopropylidene-5,6-O-sulfuryl-alpha-D-mannofuranoside (1). In a Path A, reaction of the 5,6-cyclic sulfate 1 with 2-lithio-1,3-dithiane afforded 2-(methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-mannofuranosid-6-yl)-1,3-dithiane (2). Treatment of 2 with n-butyllithium then alkyl iodide gave the corresponding 2-(methyl 5-O-alkyl-6-deoxy-2,3-O-isopropylidene-alpha-D-mannofuranosid-6-yl)-1,3-dithiane. Reaction of 2 with n-butyllithium and 5,6-cyclic sulfate 1 furnished 2-[methyl 6-deoxy-2,3-O-isopropylidene-5-O-(methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-manno-furanosid-6-yl)-alpha-D-mannofuranosid-6-yl]-1,3-dithiane. 2-(Methyl 6-deoxy-2,3-O-isopropylidene-5-O-methyl-alpha-D-mannofuranosid-6-yl)-1,3-dithiane was converted into the lithiated anion, which after treatment with alkyl halide afforded the corresponding 2-alkyl-C-(methyl 6-deoxy-2,3-O-isopropylidene-5-O-methyl-alpha-D-mannofuranosid-6-yl)-1,3-dithiane. In a Path B, 5,6-cyclic sulfate 1 reacted with 2-alkyl-2-lithio-1,3-dithiane derivatives, which led after acidic hydrolysis to 2-alkyl-2-(methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-mannofuranosid-6-yl)-1,3-dithiane accompanied by methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-lyxo-hexofuranos-5-uloside as the by-product. This methodology was applied to synthesize 2-(methyl 6-deoxy-2,3-O-isopropylidene-5-O-methyl-alpha-D-mannofuranosid-6-yl)-2-(methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-mannofuranosid-6-yl)-1,3-dithiane. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Synthesis of Ether Linked Pseudo-Oligosaccharides<i>Via</i>5,6-Cyclic Sulfate Derivatives of Protected Manno and Glucofuranose
  作者：Thierry Gourlain、Anne Wadouachi、R. Uzan、D. Beaupère

  DOI：10.1080/07328309708005739

  日期：1997.9

  C-6 ring opening of 5,6-cyclic sulfate derivatives of protected manno and glucofuranose with carbohydrate alkoxides gave ether linked pseudo-di or trisaccharides. Use of methyl 2,3-O-isopropylidene-5,6-O-sulfuryl-alpha-D-mannofuranoside 1 led to protected pseudo-disaccharide D-Glcf-(3-->6)-D-Manf-(5-->6)-D-Manf 4 and protected pseudo-trisaccharide D-Manf-(6-->3)-D-Glcf-(6-->3)-D-Glcf 11 derivatives in 66% and 41% overall yields, respectively.
• KLEIN, P. A. M. VAN DER;BOONS, G. J. P. H.;VEENEMAN, G. H.;MAREL, G. A. V+, TETRAHEDRON LETT., 30,(1989) N0, C. 5477-5480
  作者：KLEIN, P. A. M. VAN DER、BOONS, G. J. P. H.、VEENEMAN, G. H.、MAREL, G. A. V+

  DOI：——

  日期：——
• 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。