O-(tert-Butyldimethylsilyl)integerrimine | 105835-18-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: O-(tert-Butyldimethylsilyl)integerrimine
• 英文别名: (1R,4E,6R,7R,17R)-7-[tert-butyl(dimethyl)silyl]oxy-4-ethylidene-6,7-dimethyl-2,9-dioxa-14-azatricyclo[9.5.1.014,17]heptadec-11-ene-3,8-dione
• CAS: 105835-18-5
• 化学式: C₂₄H₃₉NO₅Si
• 分子量: 449.663
• InChiKey: GNHJRMCHQZTDSP-APOBKDHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.22
• 重原子数：
  31.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  65.07
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  O-(tert-Butyldimethylsilyl)integerrimine 在 氢氟酸 作用下， 以 乙腈 为溶剂， 反应 12.0h， 以67%的产率得到integerrimine
  参考文献：
  名称：

  Stereoselective synthesis of the pyrrolizidine alkaloids (-)-integerrimine and (+)-usaramine

  摘要：

  Two routes to the pyrrolizidine alkaloid (-)-integerrimine (1) are described. The first, starting from methyl (R)-(-)-3-hydroxy-2-methylpropionate, proceeded in 19 steps to integerrinecic acid lactone (5) which was transformed to the necic acid derivative 30. The latter was coupled to protected retronecine 31, and the synthesis of 1 was completed by lactonization employing Vedejs' protocol. A second, shorter synthesis of (-)-1 was accomplished via 5, starting from (R)-(+)-beta-citronellol (36). This pathway invoked Katsuki-Sharpless epoxidation of 42 for stereoselective construction of the tertiary alcohol of integerrinecic acid. A parallel sequence proceeding via the stereoisomeric epoxide 44 led to the necic acid segment 75 of the alkaloid (+)-usaramine (2). This acid was coupled to the retronecine borane 82 and then lactonized to 2.

  DOI：

  10.1021/jo00034a017
• 作为产物：
  描述：

  (4R,5R)-4,5-Dimethyl-5-(hydroxymethyl)-5-pentanolide 在 2,6-二甲基吡啶 、 六甲基磷酰三胺 、 4-二甲氨基吡啶 、 ruthenium trichloride 、 氟化铵 、 lithium hydroxide 、 正丁基锂 、 Peroxide-periodate 、 四丁基氟化铵 、 2-氯-1-甲基吡啶碘化物 、 双氧水 、 氯磷酸二乙酯 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 乙醚 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 64.33h， 生成 O-(tert-Butyldimethylsilyl)integerrimine
  参考文献：
  名称：

  Stereoselective synthesis of the pyrrolizidine alkaloids (-)-integerrimine and (+)-usaramine

  摘要：

  Two routes to the pyrrolizidine alkaloid (-)-integerrimine (1) are described. The first, starting from methyl (R)-(-)-3-hydroxy-2-methylpropionate, proceeded in 19 steps to integerrinecic acid lactone (5) which was transformed to the necic acid derivative 30. The latter was coupled to protected retronecine 31, and the synthesis of 1 was completed by lactonization employing Vedejs' protocol. A second, shorter synthesis of (-)-1 was accomplished via 5, starting from (R)-(+)-beta-citronellol (36). This pathway invoked Katsuki-Sharpless epoxidation of 42 for stereoselective construction of the tertiary alcohol of integerrinecic acid. A parallel sequence proceeding via the stereoisomeric epoxide 44 led to the necic acid segment 75 of the alkaloid (+)-usaramine (2). This acid was coupled to the retronecine borane 82 and then lactonized to 2.

  DOI：

  10.1021/jo00034a017