(4S,5R,6R)-6-Benzyloxy-4,5-dihydroxy-5,6-dihydro-4H-pyran-2-carboxylic acid methyl ester | 71200-17-4

• 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: (4S,5R,6R)-6-Benzyloxy-4,5-dihydroxy-5,6-dihydro-4H-pyran-2-carboxylic acid methyl ester
• 英文别名: methyl (2R,3R,4S)-3,4-dihydroxy-2-phenylmethoxy-3,4-dihydro-2H-pyran-6-carboxylate
• CAS: 71200-17-4
• 化学式: C₁₄H₁₆O₆
• 分子量: 280.277
• InChiKey: BZLQIIYCVNRUIK-ZKYQVNSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  85.2
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (4S,5R,6R)-6-Benzyloxy-4,5-dihydroxy-5,6-dihydro-4H-pyran-2-carboxylic acid methyl ester 在 N-溴代丁二酰亚胺(NBS) 、 水 、 silver(l) oxide 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 四氢呋喃 、 吡啶 、 氘代氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 19.5h， 生成 ((1S,3R,3aR,8aS)-3-Benzyloxy-5,5,7,7-tetraisopropyl-tetrahydro-2,4,6,8-tetraoxa-5,7-disila-azulen-1-yl)-oxo-acetic acid methyl ester
  参考文献：
  名称：

  Regio and stereoselective conversion of Δ4-uronic acids to l-Ido- and d-glucopyranosiduronic acids

  摘要：

  Synthesis of L-ido- and D-glucopyranosiduronic acids was performed starting from protected Delta(4)-uronic acids 3a-f. Bromination of the C-4,5 double bond provided the trans-diaxial bromohydrin derivatives 6a-d, which were converted to the corresponding epoxides 7a-d in high yields. Direct reduction of these epoxides using borane-tetrahydrofuran complex afforded the o-glucopyranosiduronic acids 9b-d, while Lewis acid rearrangment through the C-4 keto intermediate 10b-d afforded the L-idopyranosiduronic acids 11b-d. (C) 1997, Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(96)02514-2
• 作为产物：
  描述：

  (4S,5R,6R)-4,5-Diacetoxy-6-benzyloxy-5,6-dihydro-4H-pyran-2-carboxylic acid methyl ester 在 三乙胺 作用下， 以 甲醇 为溶剂， 反应 36.0h， 以87%的产率得到(4S,5R,6R)-6-Benzyloxy-4,5-dihydroxy-5,6-dihydro-4H-pyran-2-carboxylic acid methyl ester
  参考文献：
  名称：

  合成的δ4-尿酸酯合成单糖和糖胺聚糖衍生的二糖的构象研究。

  摘要：

  化学合成了十六种4-尿酸δ单糖。它们的羧基被保护为甲基或苄基酯，异头羟基被保护为苄基糖苷，而2和3个羟基分别被不同的取代方式保护为酯和醚衍生物。由肝素酶制备含4-尿酸δ的二糖。它们的羧基未被保护或被保护为苄基酯，并且在尿酸酯部分中的两个羟基是游离的，因为O-磺基衍生物或被酰化。通过检查质子间的邻位偶合常数，使用1 H NMR研究了这些不饱和尿酸盐单糖和二糖残基的构象。δ4-尿酸酯残基采用2H1或1H2构象。

  DOI：

  10.1016/s0008-6215(98)00118-9

文献信息

• Regio- and Stereoselective Synthesis of β-<scp>d</scp>-Gluco-, α-<scp>l</scp>-Ido-, and α-<scp>l</scp>-Altropyranosiduronic Acids from Δ⁴-Uronates
  作者：Hélène G. Bazin、Michael W. Wolff、Robert J. Linhardt

  DOI：10.1021/jo981477k

  日期：1999.1.1

  The stereoselective synthesis of beta-D-glucopyranosiduronic, alpha-L-idopyranosiduronic, and alpha-L-altropyranosiduronic acids has been performed from different Delta(4)-uronate monosaccharides. Bromination of the C-4,5 double bond provided the trans-diaxial bromohydrin derivatives, which were converted to the corresponding epoxides in high yields. Direct reduction of the epoxides using boranetetrahydrofuran complex led to the corresponding glucuronic acids in low to good yields. Glucuronic acids were also obtained in satisfactory yields through a two-steps procedure involving bromination of the epoxide with titanium(IV) bromide followed by reduction using tributyltin hydride. Lewis acid-catalyzed rearrangement of these epoxides led to the corresponding alpha-L C-4 ketopyranosides adopting the C-1(4) chair conformation. Hydride reduction afforded the alpha-L-idopyranosiduronic or the alpha-L-altropyranosiduronic acids, the stereoselectivity of the reduction being controlled by the appropriate substitution pattern.