(2S*,3R*,4R*)-3-chloro-2-ethyl-1-(p-methoxyphenyl)-4-methylpyrrolidine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (2S*,3R*,4R*)-3-chloro-2-ethyl-1-(p-methoxyphenyl)-4-methylpyrrolidine
• 英文别名: (2R,3S,4S)-3-chloro-2-ethyl-1-(4-methoxyphenyl)-4-methylpyrrolidine
• 化学式: C₁₄H₂₀ClNO
• 分子量: 253.772
• InChiKey: CZYGEWFZQOBHMQ-GDLCADMTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  cis-4-formyl-1-(p-methoxyphenyl)-3-methylazetidin-2-one 在 chlorohydroalane 、 Amberlite 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 生成 (2S*,3R*,4R*)-3-chloro-2-ethyl-1-(p-methoxyphenyl)-4-methylpyrrolidine
  参考文献：
  名称：

  Novel Diethylaluminum Chloride Promoted Reactions of the Azetidine Ring:  Efficient and Stereocontrolled Entry to Functionalized Olefins, Pyrrolidines, and Pyrroles

  摘要：

  The first examples of Lewis acid promoted fragmentation or rearrangement of the azetidine ring are reported. Azetidine precursors, cis-beta-lactams, were easily available as single cis-diastereoisomers by the Staudinger reaction. Both cis- and trans-4-formyl-beta-lactams react with the appropriate dial or dithiol under acid catalysis to yield dioxolanes or dithiolanes, while reaction with trimethyl orthoformate or benzenethiol gave 4-acetal or thioacetal beta-lactams, respectively. Azetidines were smoothly obtained by reduction of easily available beta-lactams with monochloroalane (AlH2Cl), generated in situ from LiAlH4/AlCl3. The chemical reactivity of azetidines with AlEt2Cl was further investigated. Different substituted azetidines showed varied behavior on product formation during diethylaluminum chloride promoted reactions. Azetidines having 4-methoxyphenyl or 2-furyl groups at C2 and a benzyl or allyl substituent at nitrogen efficiently reacted with AlEt2Cl to give olefins stereoselectively through a fragmentation process, while acetal or thioacetal azetidines under the standard reaction conditions afforded in a stereocontrolled manner pyrrolidines as the sole product. Furthermore, thioacetal azetidines bearing a substituent at C3 on the azetidine ring that can promote aromatization (phenoxy or exocyclic double bond) gave pyrroles by reaction with AlEt2Cl.

  DOI：

  10.1021/jo991203c

文献信息

• Novel Diethylaluminum Chloride Promoted Reactions of the Azetidine Ring:  Efficient and Stereocontrolled Entry to Functionalized Olefins, Pyrrolidines, and Pyrroles
  作者：Benito Alcaide、Pedro Almendros、Cristina Aragoncillo、Nati R. Salgado

  DOI：10.1021/jo991203c

  日期：1999.12.1

  The first examples of Lewis acid promoted fragmentation or rearrangement of the azetidine ring are reported. Azetidine precursors, cis-beta-lactams, were easily available as single cis-diastereoisomers by the Staudinger reaction. Both cis- and trans-4-formyl-beta-lactams react with the appropriate dial or dithiol under acid catalysis to yield dioxolanes or dithiolanes, while reaction with trimethyl orthoformate or benzenethiol gave 4-acetal or thioacetal beta-lactams, respectively. Azetidines were smoothly obtained by reduction of easily available beta-lactams with monochloroalane (AlH2Cl), generated in situ from LiAlH4/AlCl3. The chemical reactivity of azetidines with AlEt2Cl was further investigated. Different substituted azetidines showed varied behavior on product formation during diethylaluminum chloride promoted reactions. Azetidines having 4-methoxyphenyl or 2-furyl groups at C2 and a benzyl or allyl substituent at nitrogen efficiently reacted with AlEt2Cl to give olefins stereoselectively through a fragmentation process, while acetal or thioacetal azetidines under the standard reaction conditions afforded in a stereocontrolled manner pyrrolidines as the sole product. Furthermore, thioacetal azetidines bearing a substituent at C3 on the azetidine ring that can promote aromatization (phenoxy or exocyclic double bond) gave pyrroles by reaction with AlEt2Cl.