(1S,3R,4S,5R,6R)-7,7-dichloro-4,5-bis(phenylmethoxy)-3-(trityloxymethyl)-2-oxabicyclo[4.1.0]heptane | 195386-94-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: (1S,3R,4S,5R,6R)-7,7-dichloro-4,5-bis(phenylmethoxy)-3-(trityloxymethyl)-2-oxabicyclo[4.1.0]heptane
• CAS: 195386-94-8
• 化学式: C₄₀H₃₆Cl₂O₄
• 分子量: 651.629
• InChiKey: NERBWPDAZVZKTI-WFGAWLSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.5
• 重原子数：
  46
• 可旋转键数：
  12
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,3R,4S,5R,6R)-7,7-dichloro-4,5-bis(phenylmethoxy)-3-(trityloxymethyl)-2-oxabicyclo[4.1.0]heptane 在 甲酸 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以74%的产率得到[(1S,3R,4S,5R,6R)-7,7-dichloro-4,5-bis(phenylmethoxy)-2-oxabicyclo[4.1.0]heptan-3-yl]methanol
  参考文献：
  名称：

  Synthesis and Reactions of 1,2-Cyclopropanated Sugars

  摘要：

  Diastereospecific cyclopropanation of glycals 1, 2, 3, 4, and 41 was carried out using either dihalocarbene addition or zinc-carbenoid addition to yield 1,2-cyclopropanated sugars. Dichloro- and dibromocarbenes added stereoselectively anti to the C-3 benzyloxy group, whereas (under Simmons-Smith conditions) the cyclopropanes were formed syn to the same substituent. The reactions of these 1,2-cyclopropanated sugars to provide either ring expanded glycosides or C-2-branched chain glycosides were explored. Solvolytic ring expansion of 1,2-dibromocyclopropanated sugars with K2CO3 in refluxing methanol yielded the corresponding chiral oxepins 20-22. Electrophilic ring openings of parent cyclopropanes (14 and 17 derived from glucal 1) were carried out with different electrophiles to give functionalized 2-deoxy-2-C-branched chain glycosides. The ring openings of 14 in different solvents resulted in both alpha- and beta-anomers, whereas 17 gave exclusively the alpha-anomer.

  DOI：

  10.1021/jo970948k
• 作为产物：
  描述：

  氯仿 、 3,4-di-O-benzyl-6-O-trityl-D-glucal 在 sodium hydroxide 、 苄基三乙基氯化铵 作用下， 反应 36.0h， 以73%的产率得到(1S,3R,4S,5R,6R)-7,7-dichloro-4,5-bis(phenylmethoxy)-3-(trityloxymethyl)-2-oxabicyclo[4.1.0]heptane
  参考文献：
  名称：

  Synthesis and Reactions of 1,2-Cyclopropanated Sugars

  摘要：

  Diastereospecific cyclopropanation of glycals 1, 2, 3, 4, and 41 was carried out using either dihalocarbene addition or zinc-carbenoid addition to yield 1,2-cyclopropanated sugars. Dichloro- and dibromocarbenes added stereoselectively anti to the C-3 benzyloxy group, whereas (under Simmons-Smith conditions) the cyclopropanes were formed syn to the same substituent. The reactions of these 1,2-cyclopropanated sugars to provide either ring expanded glycosides or C-2-branched chain glycosides were explored. Solvolytic ring expansion of 1,2-dibromocyclopropanated sugars with K2CO3 in refluxing methanol yielded the corresponding chiral oxepins 20-22. Electrophilic ring openings of parent cyclopropanes (14 and 17 derived from glucal 1) were carried out with different electrophiles to give functionalized 2-deoxy-2-C-branched chain glycosides. The ring openings of 14 in different solvents resulted in both alpha- and beta-anomers, whereas 17 gave exclusively the alpha-anomer.

  DOI：

  10.1021/jo970948k

文献信息

• Synthesis and Reactions of 1,2-Cyclopropanated Sugars
  作者：C. V. Ramana、R. Murali、M. Nagarajan

  DOI：10.1021/jo970948k

  日期：1997.10.1

  Diastereospecific cyclopropanation of glycals 1, 2, 3, 4, and 41 was carried out using either dihalocarbene addition or zinc-carbenoid addition to yield 1,2-cyclopropanated sugars. Dichloro- and dibromocarbenes added stereoselectively anti to the C-3 benzyloxy group, whereas (under Simmons-Smith conditions) the cyclopropanes were formed syn to the same substituent. The reactions of these 1,2-cyclopropanated sugars to provide either ring expanded glycosides or C-2-branched chain glycosides were explored. Solvolytic ring expansion of 1,2-dibromocyclopropanated sugars with K2CO3 in refluxing methanol yielded the corresponding chiral oxepins 20-22. Electrophilic ring openings of parent cyclopropanes (14 and 17 derived from glucal 1) were carried out with different electrophiles to give functionalized 2-deoxy-2-C-branched chain glycosides. The ring openings of 14 in different solvents resulted in both alpha- and beta-anomers, whereas 17 gave exclusively the alpha-anomer.