(2S,2'S,4'S)-(-)-N-<2'-(3'-Hydroxypropyl)-4'-methylhexyl>-N-<2-(methoxymethyl)-1-pyrrolidinyl>acetamide | 150312-36-0

• 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,2'S,4'S)-(-)-N-<2'-(3'-Hydroxypropyl)-4'-methylhexyl>-N-<2-(methoxymethyl)-1-pyrrolidinyl>acetamide
• 英文别名: N-[(2S,4S)-2-(3-hydroxypropyl)-4-methylhexyl]-N-[(2S)-2-(methoxymethyl)pyrrolidin-1-yl]acetamide
• CAS: 150312-36-0
• 化学式: C₁₈H₃₆N₂O₃
• 分子量: 328.495
• InChiKey: DIOUXYFLAQXRMB-SZMVWBNQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  23
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  53
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,2'S,4'S)-(-)-N-<2'-(3'-Hydroxypropyl)-4'-methylhexyl>-N-<2-(methoxymethyl)-1-pyrrolidinyl>acetamide 在 lithium aluminium tetrahydride 、 氨 、 lithium 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 生成 (4S,6S)-4-Ethylaminomethyl-6-methyl-octan-1-ol
  参考文献：
  名称：

  Enantioselective synthesis and determination of the configuration of stenusine, the spreading agent of the beetle Stenus comma

  摘要：

  The enantioselective total synthesis of two of the four possible stereoisomers of stenusine (1), the spreading agent of the beetle Stenus comma, is described. The silyl ether-substituted aldehyde SAMP hydrazone 2 was alkylated with (S)-1-bromo-2-methylbutane (3) yielding the hydrazone 4 in high diastereomeric purity (de >95 %). By several steps including the reduction of the hydrazone functionality and the cleavage of the N-N bond of the intermediates, 4 was converted into the BOC-protected amino alcohol 6. Subsequent cyclization of 6 afforded the (S,S) diastereomer of stenusine with 96.6 % de, >99.9 % ee, and in 11.3 % overall yield. Repetition of this synthesis using the aldehyde RAMP hydrazone (R)-2 as the starting material produced (SR)-1 with 95.0 % de, >99 % ee, and in 8.2 % overall yield. The synthetic samples of 1 were employed to investigate the stereochemistry of natural stenusine by means of GC analysis on both a chiral and an achiral, stationary phase. As a result of these studies natural stenusine was found to be a mixture of all four stereoisomers in a ratio of (S,S)/(SR)/(RR)/(R:S) = 43:40:13:4.

  DOI：

  10.1021/jo00070a024
• 作为产物：
  描述：

  (S)-(+)-2-甲基溴丁烷 在 正丁基锂 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 31.0h， 生成 (2S,2'S,4'S)-(-)-N-<2'-(3'-Hydroxypropyl)-4'-methylhexyl>-N-<2-(methoxymethyl)-1-pyrrolidinyl>acetamide
  参考文献：
  名称：

  Enantioselective synthesis and determination of the configuration of stenusine, the spreading agent of the beetle Stenus comma

  摘要：

  The enantioselective total synthesis of two of the four possible stereoisomers of stenusine (1), the spreading agent of the beetle Stenus comma, is described. The silyl ether-substituted aldehyde SAMP hydrazone 2 was alkylated with (S)-1-bromo-2-methylbutane (3) yielding the hydrazone 4 in high diastereomeric purity (de >95 %). By several steps including the reduction of the hydrazone functionality and the cleavage of the N-N bond of the intermediates, 4 was converted into the BOC-protected amino alcohol 6. Subsequent cyclization of 6 afforded the (S,S) diastereomer of stenusine with 96.6 % de, >99.9 % ee, and in 11.3 % overall yield. Repetition of this synthesis using the aldehyde RAMP hydrazone (R)-2 as the starting material produced (SR)-1 with 95.0 % de, >99 % ee, and in 8.2 % overall yield. The synthetic samples of 1 were employed to investigate the stereochemistry of natural stenusine by means of GC analysis on both a chiral and an achiral, stationary phase. As a result of these studies natural stenusine was found to be a mixture of all four stereoisomers in a ratio of (S,S)/(SR)/(RR)/(R:S) = 43:40:13:4.

  DOI：

  10.1021/jo00070a024