[(E)-(S)-5-Azido-7-((1S,2S,5R)-2-isopropyl-5-methyl-cyclohexyl)-hept-6-enyloxy]-tert-butyl-diphenyl-silane | 920749-70-8

• 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: [(E)-(S)-5-Azido-7-((1S,2S,5R)-2-isopropyl-5-methyl-cyclohexyl)-hept-6-enyloxy]-tert-butyl-diphenyl-silane
• CAS: 920749-70-8
• 化学式: C₃₃H₄₉N₃OSi
• 分子量: 531.857
• InChiKey: MLIHUJYUWJKANC-SWSLVZLKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.68
• 重原子数：
  38.0
• 可旋转键数：
  12.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  57.99
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  [(E)-(S)-5-Azido-7-((1S,2S,5R)-2-isopropyl-5-methyl-cyclohexyl)-hept-6-enyloxy]-tert-butyl-diphenyl-silane 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以86%的产率得到(S)-5-(tert-Butyl-diphenyl-silanyloxy)-1-[(E)-2-((1S,2S,5R)-2-isopropyl-5-methyl-cyclohexyl)-vinyl]-pentylamine
  参考文献：
  名称：

  Cleavage of a chiral auxiliary using RCM on an especially sterically crowded alkene: Syntheses of chiral carbo- and heterocycles

  摘要：

  Chiral 1,5-, 1,6-, and 1,7-dienes generated in 3-4 steps from chiral auxiliary p-menthane-3-carboxaldehyde undergo RCM with notable discrepancies in reactivity depending on the nature and number of substituents flanking the central double bond. The chiral auxiliary is thus cleaved releasing a carbo- or heterocycle in the process. Special features concerning the RCM on these especially crowded systems are discussed. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.07.028
• 作为产物：
  描述：

  (E)-tert-butyl(6-iodohex-5-en-1-yloxy)diphenylsilane 在 正丁基锂 、 迭氮酸 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 乙醚 、 Petroleum ether 、 苯 为溶剂， 反应 7.0h， 生成 [(E)-(S)-5-Azido-7-((1S,2S,5R)-2-isopropyl-5-methyl-cyclohexyl)-hept-6-enyloxy]-tert-butyl-diphenyl-silane
  参考文献：
  名称：

  Cleavage of a chiral auxiliary using RCM on an especially sterically crowded alkene: Syntheses of chiral carbo- and heterocycles

  摘要：

  Chiral 1,5-, 1,6-, and 1,7-dienes generated in 3-4 steps from chiral auxiliary p-menthane-3-carboxaldehyde undergo RCM with notable discrepancies in reactivity depending on the nature and number of substituents flanking the central double bond. The chiral auxiliary is thus cleaved releasing a carbo- or heterocycle in the process. Special features concerning the RCM on these especially crowded systems are discussed. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.07.028

文献信息

• Sterically Biased 3,3-Sigmatropic Rearrangement of Chiral Allylic Azides: Application to the Total Syntheses of Alkaloids
  作者：Sophie Lauzon、François Tremblay、David Gagnon、Cédrickx Godbout、Christine Chabot、Catherine Mercier-Shanks、Stéphane Perreault、Hélène DeSève、Claude Spino

  DOI：10.1021/jo800817p

  日期：2008.8.1

  We describe a tandem Mitsunobu/3,3-sigmatropic rearrangement of allylic azides on a chiral auxiliary system that favors one regioisomer thanks to its exceptional steric bias. The sequence may be completed by the oxidative cleavage of the auxiliary or by a ring-closing metathesis reaction that produces a carboor heterocycle directly and a recyclable form of the chiral auxiliary. Applications of the methodology to the total synthesis of (+)-coniine, (+)-lentiginosin, and (+)-pumiliotoxin C are reported.