methyl 3-O-benzyl-2,4,6-trideoxy-α-D-threo-hept-6-ynopyranoside | 614752-14-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 3-O-benzyl-2,4,6-trideoxy-α-D-threo-hept-6-ynopyranoside
• 英文别名: (2S,4S,6S)-2-ethynyl-6-methoxy-4-phenylmethoxyoxane
• CAS: 614752-14-6
• 化学式: C₁₅H₁₈O₃
• 分子量: 246.306
• InChiKey: QXSHOERAZDTPHD-ILXRZTDVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 3-O-benzyl-2,4,6-trideoxy-α-D-threo-hept-6-ynopyranoside 在 palladium diacetate samarium diiodide 、 三丁基膦 作用下， 以 四氢呋喃 为溶剂， 反应 0.1h， 生成 (1R,2S,4S)-4-benzyloxy-2-ethynylcyclopentanol
  参考文献：
  名称：

  Substituent effects on the SmI2/Pd(0)-promoted carbohydrate ring-contraction of 5-alkynylpyranosides

  摘要：

  The effect of substituents on the reactivity and stereoselectivity of the SmI2/Pd(0)-promoted ring-contraction of 5-alkynylpyranosides has been examined using substrates substituted only at selected positions. While formation of 2-ethynylcyclopentanols takes place efficiently, an internal alkyne did not afford the expected product. The presence of peripheral alkoxy substituents leads to variable stereoselectivities that depend on the number and orientation of such groups. Thus, an isolated OBn substituent at C(3) (carbohydrate numbering) exerts a significant stereochemical control while additional substitution with the same group at C(4) either enhances or drastically reduces stereoselectivity depending on its orientation (alpha or beta, respectively). (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)01103-7
• 作为产物：
  描述：

  Α-D-乳酸吡喃糖苷甲酯 在 咪唑 、 草酰氯 、 偶氮二异丁腈 、 四丁基氟化铵 、 三正丁基氢锡 、 sodium hydride 、 二正丁基氧化锡 、 potassium carbonate 、 二甲基亚砜 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 苯 为溶剂， 反应 104.0h， 生成 methyl 3-O-benzyl-2,4,6-trideoxy-α-D-threo-hept-6-ynopyranoside
  参考文献：
  名称：

  Substituent effects on the SmI2/Pd(0)-promoted carbohydrate ring-contraction of 5-alkynylpyranosides

  摘要：

  The effect of substituents on the reactivity and stereoselectivity of the SmI2/Pd(0)-promoted ring-contraction of 5-alkynylpyranosides has been examined using substrates substituted only at selected positions. While formation of 2-ethynylcyclopentanols takes place efficiently, an internal alkyne did not afford the expected product. The presence of peripheral alkoxy substituents leads to variable stereoselectivities that depend on the number and orientation of such groups. Thus, an isolated OBn substituent at C(3) (carbohydrate numbering) exerts a significant stereochemical control while additional substitution with the same group at C(4) either enhances or drastically reduces stereoselectivity depending on its orientation (alpha or beta, respectively). (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)01103-7

文献信息

• Substituent effects on the SmI2/Pd(0)-promoted carbohydrate ring-contraction of 5-alkynylpyranosides
  作者：José M. Aurrecoechea、Jesús H. Gil、Beatriz López

  DOI：10.1016/s0040-4020(03)01103-7

  日期：2003.9

  The effect of substituents on the reactivity and stereoselectivity of the SmI2/Pd(0)-promoted ring-contraction of 5-alkynylpyranosides has been examined using substrates substituted only at selected positions. While formation of 2-ethynylcyclopentanols takes place efficiently, an internal alkyne did not afford the expected product. The presence of peripheral alkoxy substituents leads to variable stereoselectivities that depend on the number and orientation of such groups. Thus, an isolated OBn substituent at C(3) (carbohydrate numbering) exerts a significant stereochemical control while additional substitution with the same group at C(4) either enhances or drastically reduces stereoselectivity depending on its orientation (alpha or beta, respectively). (C) 2003 Elsevier Ltd. All rights reserved.