1β-(p-toluenesulfonamido)-2β,3β-epoxy-4α-chloro-6α-(benzyloxy)-2-cycloheptene | 132622-32-3

• 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: 1β-(p-toluenesulfonamido)-2β,3β-epoxy-4α-chloro-6α-(benzyloxy)-2-cycloheptene
• 英文别名: N-[(1R,2R,4R,6R,7R)-6-chloro-4-phenylmethoxy-8-oxabicyclo[5.1.0]octan-2-yl]-4-methylbenzenesulfonamide
• CAS: 132622-32-3
• 化学式: C₂₁H₂₄ClNO₄S
• 分子量: 421.945
• InChiKey: YGVCQFUNYDYOKA-KTIPNOMGSA-N

物化性质

• 沸点：
  579.3±60.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  76.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1β-(p-toluenesulfonamido)-2β,3β-epoxy-4α-chloro-6α-(benzyloxy)-2-cycloheptene 在 palladium on activated charcoal 盐酸 、 萘 、 氢气 、 sodium 、 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 68.5h， 生成 Scopine
  参考文献：
  名称：

  Stereocontrolled epoxidations of cycloheptene derivatives in the palladium-catalyzed route to tropane alkaloids. Total syntheses of scopine and pseudoscopine

  摘要：

  Stereoselective total syntheses of the tropane alkaloids scopine (1) and pseudoscopine (3) have been developed via the chloroacetoxylation approach. Palladium-catalyzed 1,4-chloroacetoxylation of diene 6 afforded the key intermediate 7. Subsequent substitution of the allylic chloride by TsNH-with either retention (Pd(O) catalysis) or inversion (S(N)2) of configuration gave 10 and 16, respectively. The epoxy oxygen was introduced syn to the nitrogen function prior to cyclization by utilizing the syn-directive effect of the allylic sulfonamido group in the epoxidation. Cyclization of the epoxides 12 and 21, followed by replacement of the tosyl group by a methyl group and subsequent debenzylation, afforded the title compounds 1 and 3, respectively.

  DOI：

  10.1021/jo00008a037
• 作为产物：
  描述：

  sodium p-toluenesulfonamide 在 四(三苯基膦)钯 2,4,6-三甲基吡啶 、 甲基磺酰氯 、 间氯过氧苯甲酸 、 lithium chloride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 52.0h， 生成 1β-(p-toluenesulfonamido)-2β,3β-epoxy-4α-chloro-6α-(benzyloxy)-2-cycloheptene
  参考文献：
  名称：

  Stereocontrolled epoxidations of cycloheptene derivatives in the palladium-catalyzed route to tropane alkaloids. Total syntheses of scopine and pseudoscopine

  摘要：

  Stereoselective total syntheses of the tropane alkaloids scopine (1) and pseudoscopine (3) have been developed via the chloroacetoxylation approach. Palladium-catalyzed 1,4-chloroacetoxylation of diene 6 afforded the key intermediate 7. Subsequent substitution of the allylic chloride by TsNH-with either retention (Pd(O) catalysis) or inversion (S(N)2) of configuration gave 10 and 16, respectively. The epoxy oxygen was introduced syn to the nitrogen function prior to cyclization by utilizing the syn-directive effect of the allylic sulfonamido group in the epoxidation. Cyclization of the epoxides 12 and 21, followed by replacement of the tosyl group by a methyl group and subsequent debenzylation, afforded the title compounds 1 and 3, respectively.

  DOI：

  10.1021/jo00008a037

文献信息

• Stereocontrolled epoxidations of cycloheptene derivatives in the palladium-catalyzed route to tropane alkaloids. Total syntheses of scopine and pseudoscopine
  作者：Hans E. Schink、Helena Pettersson、Jan E. Baeckvall

  DOI：10.1021/jo00008a037

  日期：1991.4

  Stereoselective total syntheses of the tropane alkaloids scopine (1) and pseudoscopine (3) have been developed via the chloroacetoxylation approach. Palladium-catalyzed 1,4-chloroacetoxylation of diene 6 afforded the key intermediate 7. Subsequent substitution of the allylic chloride by TsNH-with either retention (Pd(O) catalysis) or inversion (S(N)2) of configuration gave 10 and 16, respectively. The epoxy oxygen was introduced syn to the nitrogen function prior to cyclization by utilizing the syn-directive effect of the allylic sulfonamido group in the epoxidation. Cyclization of the epoxides 12 and 21, followed by replacement of the tosyl group by a methyl group and subsequent debenzylation, afforded the title compounds 1 and 3, respectively.