<2S-<2α(2R^*,4R^*),6α>>-2-<1-(Azidomethyl)-3,3-dimethyl-2,4-dioxolan-5-yl>-6-methoxy-4,5-dihydro-2H-pyran-3(6H)-one | 147646-00-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: <2S-<2α(2R^*,4R^*),6α>>-2-<1-(Azidomethyl)-3,3-dimethyl-2,4-dioxolan-5-yl>-6-methoxy-4,5-dihydro-2H-pyran-3(6H)-one
• 英文别名: (2S,6R)-2-[(4R,5S)-5-(azidomethyl)-2,2-dimethyl-1,3-dioxolan-4-yl]-6-methoxyoxan-3-one
• CAS: 147646-00-2
• 化学式: C₁₂H₁₉N₃O₅
• 分子量: 285.3
• InChiKey: WSWDDEKKUYBQNT-LNFKQOIKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  68.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  <2S-<2α(2R^*,4R^*),6α>>-2-<1-(Azidomethyl)-3,3-dimethyl-2,4-dioxolan-5-yl>-6-methoxy-4,5-dihydro-2H-pyran-3(6H)-one 在 palladium on activated charcoal 盐酸 、 氢气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 25.0 ℃ 、482.63 kPa 条件下， 反应 58.0h， 生成 (6S,7R,8R,8aS)-6,7,8-trihydroxy-indolizidine
  参考文献：
  名称：

  Facile asymmetric syntheses of 1-deoxycastanospermine and 1-deoxy-8a-epi-castanospermine

  摘要：

  The asymmetric syntheses of 1-deoxycastanospermine (6) and 1-deoxy-8a-epi-castanospermine (7) have been completed. A key step in these syntheses was the stereoselective addition of 2-furyllithium to the 4-O-tert-butyldiphenylsilyl-protected threose derivative 13 to give the C(7)-C(8) syn-adduct 14 as the major product. The diastereoselectivity of this reaction is particularly noteworthy since the related addition of 2-furyllithium to the corresponding 4-O-benzyl-protected aldehyde 8 proceeded in the opposite stereochemical sense to give primarily the C(7)-C(8) anti-adduct 10. Oxidation of the furan ring in 14 followed by refunctionalization led to the azido ketone 20, which was then converted into the imine 22 by several procedures. Depending upon the reaction conditions, stereoselective reduction of 22 furnished primarily either 23 or 24. Hydrolysis of the pyranoid acetal moiety in 23 and 24 followed by reductive amination gave 6 or 7, respectively.

  DOI：

  10.1021/jo00062a035
• 作为产物：
  描述：

  4-O-(tert-butyldiphenylsilyl)-2,3-O-isopropylidene-L-threitol 在 N-甲基吗啉 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 正丁基锂 、 sodium azide 、 草酰氯 、 bis(acetylacetonate)oxovanadium 、 乙醇 、 4 A molecular sieve 、 四丁基氟化铵 、 potassium tri-sec-butyl-borohydride 、 二甲基亚砜 、 三乙胺 、 silver(l) oxide 、 zinc dibromide 作用下， 以 四氢呋喃 、 异辛烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 77.5h， 生成 <2S-<2α(2R^*,4R^*),6α>>-2-<1-(Azidomethyl)-3,3-dimethyl-2,4-dioxolan-5-yl>-6-methoxy-4,5-dihydro-2H-pyran-3(6H)-one
  参考文献：
  名称：

  Facile asymmetric syntheses of 1-deoxycastanospermine and 1-deoxy-8a-epi-castanospermine

  摘要：

  The asymmetric syntheses of 1-deoxycastanospermine (6) and 1-deoxy-8a-epi-castanospermine (7) have been completed. A key step in these syntheses was the stereoselective addition of 2-furyllithium to the 4-O-tert-butyldiphenylsilyl-protected threose derivative 13 to give the C(7)-C(8) syn-adduct 14 as the major product. The diastereoselectivity of this reaction is particularly noteworthy since the related addition of 2-furyllithium to the corresponding 4-O-benzyl-protected aldehyde 8 proceeded in the opposite stereochemical sense to give primarily the C(7)-C(8) anti-adduct 10. Oxidation of the furan ring in 14 followed by refunctionalization led to the azido ketone 20, which was then converted into the imine 22 by several procedures. Depending upon the reaction conditions, stereoselective reduction of 22 furnished primarily either 23 or 24. Hydrolysis of the pyranoid acetal moiety in 23 and 24 followed by reductive amination gave 6 or 7, respectively.

  DOI：

  10.1021/jo00062a035

文献信息

• Facile asymmetric syntheses of 1-deoxycastanospermine and 1-deoxy-8a-epi-castanospermine
  作者：Stephen F. Martin、Hui Ju Chen、Chih Ping Yang

  DOI：10.1021/jo00062a035

  日期：1993.5

  The asymmetric syntheses of 1-deoxycastanospermine (6) and 1-deoxy-8a-epi-castanospermine (7) have been completed. A key step in these syntheses was the stereoselective addition of 2-furyllithium to the 4-O-tert-butyldiphenylsilyl-protected threose derivative 13 to give the C(7)-C(8) syn-adduct 14 as the major product. The diastereoselectivity of this reaction is particularly noteworthy since the related addition of 2-furyllithium to the corresponding 4-O-benzyl-protected aldehyde 8 proceeded in the opposite stereochemical sense to give primarily the C(7)-C(8) anti-adduct 10. Oxidation of the furan ring in 14 followed by refunctionalization led to the azido ketone 20, which was then converted into the imine 22 by several procedures. Depending upon the reaction conditions, stereoselective reduction of 22 furnished primarily either 23 or 24. Hydrolysis of the pyranoid acetal moiety in 23 and 24 followed by reductive amination gave 6 or 7, respectively.