2-(2-chloroethyl)-4,5-methylenedioxybenzaldehyde | 1356336-79-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 2-(2-chloroethyl)-4,5-methylenedioxybenzaldehyde
• 英文别名: 6-(2-chloroethyl)-1,3-benzodioxole-5-carbaldehyde
• CAS: 1356336-79-2
• 化学式: C₁₀H₉ClO₃
• 分子量: 212.633
• InChiKey: MCUGSYHPSRIMCN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.01
• 重原子数：
  14.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2-(2-chloroethyl)-4,5-methylenedioxybenzaldehyde 在 titanium(IV) tetraethanolate 、 三氟乙酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 8.0h， 生成 (1S)-1-[3,4-dimethoxy-2-(S)-p-tolylsulfinyl]benzyl-6,7-methylenedioxy-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  Asymmetric synthesis of (S)-(−)-tetrahydropalmatine and (S)-(−)-canadine via a sulfinyl-directed Pictet–Spengler cyclization

  摘要：

  (S)-(-)-Tetrahydropalmatine 2 and (S)-(-)-canadine 4 were synthesized in three steps from (S)-6, in 33% and 34% overall yield, respectively. Thus, condensation of the (S)-(E)-sulfinylimines 10 and 11 with the carbanion derived from (S)-6 gave the tetrahydroisoquinolines 12 and 13, respectively, which upon TFA induced N-desulfinylation, and subsequent microwave assisted Pictet-Spengler cyclization effected both cyclization and C-desulfinylation producing (S)-(-)-tetrahydropalmatine 2 and (S)-(-)-canadine 4 in optically pure form. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.11.046
• 作为产物：
  描述：

  6,7-methylenedioxy-1-ethoxyisochroman 在 乙酰氯 作用下， 反应 5.0h， 以1.55 g的产率得到2-(2-chloroethyl)-4,5-methylenedioxybenzaldehyde
  参考文献：
  名称：

  Asymmetric synthesis of (S)-(−)-tetrahydropalmatine and (S)-(−)-canadine via a sulfinyl-directed Pictet–Spengler cyclization

  摘要：

  (S)-(-)-Tetrahydropalmatine 2 and (S)-(-)-canadine 4 were synthesized in three steps from (S)-6, in 33% and 34% overall yield, respectively. Thus, condensation of the (S)-(E)-sulfinylimines 10 and 11 with the carbanion derived from (S)-6 gave the tetrahydroisoquinolines 12 and 13, respectively, which upon TFA induced N-desulfinylation, and subsequent microwave assisted Pictet-Spengler cyclization effected both cyclization and C-desulfinylation producing (S)-(-)-tetrahydropalmatine 2 and (S)-(-)-canadine 4 in optically pure form. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.11.046

文献信息

• 一种手性(-)-三尖杉碱的合成方法及其中间体
  申请人：中国科学院上海有机化学研究所

  公开号：CN109776506B

  公开（公告）日：2022-06-21

  本发明公开了一种手性(‑)‑三尖杉碱的合成方法及其中间体。本发明的合成方法包括如下步骤：在溶剂中，在路易斯酸的作用下，将化合物A进行如下所示的重排反应得到化合物B即可。本发明的合成方法以工业化原料呋喃为起始原料，通过10步得到手性的三尖杉碱，反应收率高，操作简便，有望应用于工业生产。
• Asymmetric synthesis of (S)-(−)-tetrahydropalmatine and (S)-(−)-canadine via a sulfinyl-directed Pictet–Spengler cyclization
  作者：Virginia M. Mastranzo、José Luis Olivares Romero、Francisco Yuste、Benjamín Ortiz、Rubén Sánchez-Obregón、José L. García Ruano

  DOI：10.1016/j.tet.2011.11.046

  日期：2012.1

  (S)-(-)-Tetrahydropalmatine 2 and (S)-(-)-canadine 4 were synthesized in three steps from (S)-6, in 33% and 34% overall yield, respectively. Thus, condensation of the (S)-(E)-sulfinylimines 10 and 11 with the carbanion derived from (S)-6 gave the tetrahydroisoquinolines 12 and 13, respectively, which upon TFA induced N-desulfinylation, and subsequent microwave assisted Pictet-Spengler cyclization effected both cyclization and C-desulfinylation producing (S)-(-)-tetrahydropalmatine 2 and (S)-(-)-canadine 4 in optically pure form. (C) 2011 Elsevier Ltd. All rights reserved.