(5Z,11S)-11-{[(tert-butoxy)carbonyl](2-[(tert-butyl)dimethylsilyloxy]ethyl)amino}tetradec-5-enoic acid | 189251-26-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (5Z,11S)-11-{[(tert-butoxy)carbonyl](2-[(tert-butyl)dimethylsilyloxy]ethyl)amino}tetradec-5-enoic acid
• 英文别名: (S)-(Z)-11-[[2-(tert-butyldimethylsilanyloxy)ethyl](dimethylethoxycarbonyl)amino]tetradec-5-enoic acid；(Z,11S)-11-[2-[tert-butyl(dimethyl)silyl]oxyethyl-[(2-methylpropan-2-yl)oxycarbonyl]amino]tetradec-5-enoic acid
• CAS: 189251-26-1
• 化学式: C₂₇H₅₃NO₅Si
• 分子量: 499.807
• InChiKey: HTKSTQNZCFSKSP-BLSBEMRDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.79
• 重原子数：
  34
• 可旋转键数：
  19
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  76.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (5Z,11S)-11-{[(tert-butoxy)carbonyl](2-[(tert-butyl)dimethylsilyloxy]ethyl)amino}tetradec-5-enoic acid 在 4-二甲氨基吡啶 、 四丁基氟化铵 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.5h， 生成 (S)-(5Z,8Z)-11-[[2-(tert-butyldiphenylsilanyloxy)ethyl](dimethylethoxycarbonyl)amino]tetradeca-5,8-dienoic acid 2-[((S)-(Z)-10-allyloxycarbonyl-1-propyldec-6-enyl)tert-butoxycarbonylamino]ethyl ester
  参考文献：
  名称：

  Synthesis of Unsaturated Polyazamacrolides from the Ladybird Beetle Subcoccinella vigintiquatuorpunctata

  摘要：

  The pupal defensive secretion of the ladybird beetle Subcoccinella vigintiquatuorpunctata consists of a mixture of macrocyclic polyamines (polyazamacrolides, PAMLs) dominated by three dimeric, 30-membered bislactones (1, 2, and 3), which represent the three possible head-to-tail combinations of the two building blocks (S)-(Z)-11-(2-hydroxyethylamino)-5-tetradecenoic acid (4) and (S)-(5Z,8Z)-11-(2-hydroxyethylamino)-5,8-tetradecadienoic acid (5). We now report the synthesis of these three alkaloids via a route involving the nucleophilic opening of a chiral aziridine as a common step.

  DOI：

  10.1021/jo001200w
• 作为产物：
  描述：

  L-正缬氨酸 在 吡啶 、 copper(l) iodide 、 锂硼氢 、 三甲基氯硅烷 、 萘 、 sodium 、 sodium hydride 、 potassium carbonate 、 臭氧 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 乙醚 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 154.0h， 生成 (5Z,11S)-11-{[(tert-butoxy)carbonyl](2-[(tert-butyl)dimethylsilyloxy]ethyl)amino}tetradec-5-enoic acid
  参考文献：
  名称：

  大环昆虫生物碱的合成

  摘要：

  使用对映体纯的 α-氨基酸作为手性池起始材料，通过有效的合成路线以对映体纯的形式制备在两种瓢虫（Epilachna 属）的蛹分泌物中发现的大环内酯生物碱。使用 Mukaiyama 的大环内酯化条件以良好的产率合成了含有多达 98 个原子的大环。

  DOI：

  10.1002/1522-2675(20000906)83:9<2594::aid-hlca2594>3.0.co;2-h

文献信息

• Absolute configuration of insect-produced epilachnene
  作者：Jay J. Farmer、Athula B. Attygalle、Scott R. Smedley、Thomas Eisner、Jerrold Meinwald

  DOI：10.1016/s0040-4039(97)00490-5

  日期：1997.4

  Samples of (R) and (S)-epilachnene [(5Z)-11-propyl-12-azacyclotetradec-5-en-14-olide] were synthesized from (R) and(S)-norvaline. The diastereomeric alpha-methoxy-alpha-trifluoromethylphenylacetyl amides of these synthetic samples, prepared using (S) alpha-methoxy-alpha-trifluoromethylphenylacetyl chloride, were well resolved by gas chromatography. Analogous derivatization and gas chromatographic analysis of a sample of epilachnene from the pupal secretion of the coccinellid beetle, Epilachna varivestis, established that the natural product is (S)-epilachnene. (C) 1997 Elsevier Science Ltd.
• Synthesis of Unsaturated Polyazamacrolides from the Ladybird Beetle <i>Subcoccinella </i><i>v</i><i>igintiquatuorpunctata</i>
  作者：Matthew R. Gronquist、Jerrold Meinwald

  DOI：10.1021/jo001200w

  日期：2001.2.1

  The pupal defensive secretion of the ladybird beetle Subcoccinella vigintiquatuorpunctata consists of a mixture of macrocyclic polyamines (polyazamacrolides, PAMLs) dominated by three dimeric, 30-membered bislactones (1, 2, and 3), which represent the three possible head-to-tail combinations of the two building blocks (S)-(Z)-11-(2-hydroxyethylamino)-5-tetradecenoic acid (4) and (S)-(5Z,8Z)-11-(2-hydroxyethylamino)-5,8-tetradecadienoic acid (5). We now report the synthesis of these three alkaloids via a route involving the nucleophilic opening of a chiral aziridine as a common step.
• Synthesis of Macrocyclic Insect-Derived Alkaloids
  作者：Jay J. Farmer、Frank C. Schroeder、Jerrold Meinwald

  DOI：10.1002/1522-2675(20000906)83:9<2594::aid-hlca2594>3.0.co;2-h

  日期：2000.9.6

  Macrocyclic lactonic alkaloids found in the pupal secretions of two species of a coccinellid beetle (genus Epilachna) were prepared in enantiomerically pure form via an efficient synthetic route using enantiomerically pure α-amino acids as chiral-pool starting materials. Macrocycles with rings containing up to 98 atoms were synthesized in good yield using Mukaiyama's macrolactonization conditions.

  使用对映体纯的 α-氨基酸作为手性池起始材料，通过有效的合成路线以对映体纯的形式制备在两种瓢虫（Epilachna 属）的蛹分泌物中发现的大环内酯生物碱。使用 Mukaiyama 的大环内酯化条件以良好的产率合成了含有多达 98 个原子的大环。