(5S,6R)-(-)-1-<(1R)-1-(2,6-dichlorophenyl)ethyl>-5-(4-hydroxybut-2-yl)pyrrolidinone | 134457-73-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (5S,6R)-(-)-1-<(1R)-1-(2,6-dichlorophenyl)ethyl>-5-(4-hydroxybut-2-yl)pyrrolidinone
• 英文别名: (5S)-1-[(1R)-1-(2,6-dichlorophenyl)ethyl]-5-[(2R)-4-hydroxybutan-2-yl]pyrrolidin-2-one
• CAS: 134457-73-1
• 化学式: C₁₆H₂₁Cl₂NO₂
• 分子量: 330.254
• InChiKey: LEXVKXRVSYIHFO-GYSYKLTISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.06
• 重原子数：
  21.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  40.54
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (5S,6R)-(-)-1-<(1R)-1-(2,6-dichlorophenyl)ethyl>-5-(4-hydroxybut-2-yl)pyrrolidinone 在 palladium on activated charcoal 盐酸 、 potassium fluoride 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 (COCl₂)2 、 camphor-10-sulfonic acid 、 氢气 、 叔丁基锂 、 二甲基亚砜 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 59.08h， 生成 [5R,8R,8aS]-(-)-8-methyl-5-(pent-4-ynyl)octahydroindolizine
  参考文献：
  名称：

  Enantioselective total syntheses of indolizidine alkaloids (-)-205A and (-)-235B

  摘要：

  Enantioselective total syntheses of indolizidine alkaloids (-)-205A and (-)-235B are described. The syntheses proceed via a common late-stage intermediate, alpha-aminonitrile 1. Absolute stereochemical control over the C8 and C8a stereocenters in these materials was achieved by a stereoselective crotylation reaction between chiral acyliminium ion (R)-3b and crotylmagnesium chloride. The selectivity of this reaction, which produced the (future)-8R,8aS configuration was complementary to the result obtained by crotylation of acyliminium ion (S)-3a with trans-crotyltrimethylsilane, which produced predominantly an adduct with the (future)-8S,8aS configuration. This latter crotyl lactam was converted to two additional diastereomers of alkaloid 205A. Comparison of the H-1 and C-13 NMR and optical rotation values of the four synthetic diastereomers of 205A with literature values supported the proposed assignment of the absolute and relative configuration of (-)-205A. The C-13 spectrum of synthetic (5R,8R,8aS)-235B was identical with that of natural 235B and supported the proposed assignment of relative configuration of the alkaloid. The optical rotation differed in sign and magnitude from the published value. Revised values of the optical rotations of (-)-205A and (-)-235B are suggested. This work constitutes the first enantioselective syntheses of 205A and 235B, which were prepared in 15 and 14 steps, respectively, from succinic anhydride, in an average overall yield of 17%.

  DOI：

  10.1021/jo00016a013
• 作为产物：
  描述：

  (5R)-(-)-<(1R)-1-(2,6-dichlorophenyl)ethyl>-5-(p-toluenesulfonyl)pyrrolidinone 在 sodium hydroxide 、 双氧水 、 二(3-甲基丁烷-2-基)硼烷 、 zinc dibromide 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 6.0h， 生成 (5S,6R)-(-)-1-<(1R)-1-(2,6-dichlorophenyl)ethyl>-5-(4-hydroxybut-2-yl)pyrrolidinone
  参考文献：
  名称：

  Enantioselective total syntheses of indolizidine alkaloids (-)-205A and (-)-235B

  摘要：

  Enantioselective total syntheses of indolizidine alkaloids (-)-205A and (-)-235B are described. The syntheses proceed via a common late-stage intermediate, alpha-aminonitrile 1. Absolute stereochemical control over the C8 and C8a stereocenters in these materials was achieved by a stereoselective crotylation reaction between chiral acyliminium ion (R)-3b and crotylmagnesium chloride. The selectivity of this reaction, which produced the (future)-8R,8aS configuration was complementary to the result obtained by crotylation of acyliminium ion (S)-3a with trans-crotyltrimethylsilane, which produced predominantly an adduct with the (future)-8S,8aS configuration. This latter crotyl lactam was converted to two additional diastereomers of alkaloid 205A. Comparison of the H-1 and C-13 NMR and optical rotation values of the four synthetic diastereomers of 205A with literature values supported the proposed assignment of the absolute and relative configuration of (-)-205A. The C-13 spectrum of synthetic (5R,8R,8aS)-235B was identical with that of natural 235B and supported the proposed assignment of relative configuration of the alkaloid. The optical rotation differed in sign and magnitude from the published value. Revised values of the optical rotations of (-)-205A and (-)-235B are suggested. This work constitutes the first enantioselective syntheses of 205A and 235B, which were prepared in 15 and 14 steps, respectively, from succinic anhydride, in an average overall yield of 17%.

  DOI：

  10.1021/jo00016a013