(1R,5S,9Z,11R,14S)-14-[tert-butyl(dimethyl)silyl]oxy-5-methyl-4,15-dioxabicyclo[9.3.1]pentadec-9-en-3-one | 1240505-15-0

• 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: (1R,5S,9Z,11R,14S)-14-[tert-butyl(dimethyl)silyl]oxy-5-methyl-4,15-dioxabicyclo[9.3.1]pentadec-9-en-3-one
• CAS: 1240505-15-0
• 化学式: C₂₀H₃₆O₄Si
• 分子量: 368.589
• InChiKey: NZHXSEGISWJNTL-ZZEHMKCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.99
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,5S,9Z,11R,14S)-14-[tert-butyl(dimethyl)silyl]oxy-5-methyl-4,15-dioxabicyclo[9.3.1]pentadec-9-en-3-one 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以85%的产率得到(1R,5S,11R,14S)-14-hydroxy-5-methyl-4,15-dioxabicyclo-[9.3.1]pentadec-9(Z)-en-3-one
  参考文献：
  名称：

  Stereoselective formal synthesis of aspergillide A

  摘要：

  The stereoselective formal synthesis of aspergillide A (1), a cytotoxic 14-membered macrolide, is disclosed. The key intermediate, a trisubstituted tetrahydropyran core is prepared by SmI(2)-induced intramolecular reductive cyclization as well as by using sequential alpha-aminooxylation, Homer-Wadsworth-Emmons olefination, and followed by Oxa-Michael cyclization. Other notable transformations in the synthesis include the use of Jacobsen's hydrolytic kinetic resolution, esterification, ring-closing metathesis (RCM), and cross-metathesis (CM) reactions. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2010.06.013
• 作为产物：
  描述：

  [(2S)-hept-6-en-2-yl] 2-[(2R,3S,6R)-3-[tert-butyl(dimethyl)silyl]oxy-6-ethenyloxan-2-yl]acetate 在 Grubbs catalyst first generation 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以90%的产率得到(1R,5S,9Z,11R,14S)-14-[tert-butyl(dimethyl)silyl]oxy-5-methyl-4,15-dioxabicyclo[9.3.1]pentadec-9-en-3-one
  参考文献：
  名称：

  Stereoselective formal synthesis of aspergillide A

  摘要：

  The stereoselective formal synthesis of aspergillide A (1), a cytotoxic 14-membered macrolide, is disclosed. The key intermediate, a trisubstituted tetrahydropyran core is prepared by SmI(2)-induced intramolecular reductive cyclization as well as by using sequential alpha-aminooxylation, Homer-Wadsworth-Emmons olefination, and followed by Oxa-Michael cyclization. Other notable transformations in the synthesis include the use of Jacobsen's hydrolytic kinetic resolution, esterification, ring-closing metathesis (RCM), and cross-metathesis (CM) reactions. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2010.06.013

文献信息

• Stereoselective formal synthesis of aspergillide A
  作者：Gowravaram Sabitha、D. Vasudeva Reddy、A. Senkara Rao、J.S. Yadav

  DOI：10.1016/j.tetlet.2010.06.013

  日期：2010.8

  The stereoselective formal synthesis of aspergillide A (1), a cytotoxic 14-membered macrolide, is disclosed. The key intermediate, a trisubstituted tetrahydropyran core is prepared by SmI(2)-induced intramolecular reductive cyclization as well as by using sequential alpha-aminooxylation, Homer-Wadsworth-Emmons olefination, and followed by Oxa-Michael cyclization. Other notable transformations in the synthesis include the use of Jacobsen's hydrolytic kinetic resolution, esterification, ring-closing metathesis (RCM), and cross-metathesis (CM) reactions. (C) 2010 Elsevier Ltd. All rights reserved.