1β-acetoxy-4β-chloro-6α-(benzyloxy)-2-cycloheptene | 115522-57-1

• 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-acetoxy-4β-chloro-6α-(benzyloxy)-2-cycloheptene
• 英文别名: [(1S,4R,6S)-4-chloro-6-phenylmethoxycyclohept-2-en-1-yl] acetate
• CAS: 115522-57-1；150338-86-6
• 化学式: C₁₆H₁₉ClO₃
• 分子量: 294.778
• InChiKey: ILSMKLIYDFDHNK-ARFHVFGLSA-N

物化性质

• 沸点：
  389.2±42.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1β-acetoxy-4β-chloro-6α-(benzyloxy)-2-cycloheptene 在 palladium on activated charcoal 咪唑 、 sodium hydroxide 、 萘 、 甲烷磺酸 、 四丁基氟化铵 、 氢气 、 sodium 、 potassium carbonate 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 氯仿 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， -78.0~80.0 ℃ 、101.33 kPa 条件下， 反应 164.58h， 生成 pseudoscopine
  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：

  环庚-3,5-二烯-1-醇 在 palladium diacetate sodium hydride 、 溶剂黄146 、 对苯醌 、 lithium chloride 作用下， 以 四氢呋喃 、 溶剂黄146 为溶剂， 反应 51.0h， 生成 1β-acetoxy-4β-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 synthesis of tropanol derivatives via palladium -catalyzed reactions
  作者：J.E. Bäckvall、Z.D. Renko、S.E. Byström

  DOI：10.1016/s0040-4039(00)95578-3

  日期：——

  A general method for the transformation of 1,3-cycloheptadienes to tropane alkaloid derivatives was developed. The procedure was applied to the stereocontrolled synthesis of the exo- and endo-tropanol derivatives and . The approach is based on a dual stereocontrol in the 1,4-functionalization of conjugated dienes.

  开发了将1，3-环庚二烯转化为托烷生物碱衍生物的通用方法。该方法被用于立体控制合成外，对内醇衍生物和。该方法基于共轭二烯的1,4-官能化中的双重立体控制。
• Stereocontrolled lactonization reactions via palladium-catalyzed 1,4-addition to conjugated dienes
  作者：Jan E. Baeckvall、Kenneth L. Granberg、Pher G. Andersson、Roberto Gatti、Adolf Gogoll

  DOI：10.1021/jo00072a029

  日期：1993.9
• Bckvall Jan-E., Granberg Kenneth L., Andersson Pher G., Gatti Roberto, Go+, J. Org. Chem, 58 (1993) N 20, S 5445-5451
  作者：Bckvall Jan-E., Granberg Kenneth L., Andersson Pher G., Gatti Roberto, Go+

  DOI：——

  日期：——