N-[(E,3S)-7-[tert-butyl(dimethyl)silyl]oxy-1-[(1S,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oct-1-en-3-yl]but-3-enamide | 1042908-34-8

• 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: N-[(E,3S)-7-[tert-butyl(dimethyl)silyl]oxy-1-[(1S,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oct-1-en-3-yl]but-3-enamide
• CAS: 1042908-34-8
• 化学式: C₂₈H₅₃NO₂Si
• 分子量: 463.82
• InChiKey: IHSXXKMQYNXNFE-ZSYYWTNWSA-N

物化性质

• 沸点：
  536.5±50.0 °C(predicted)
• 密度：
  0.916±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.89
• 重原子数：
  32
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-[(E,3S)-7-[tert-butyl(dimethyl)silyl]oxy-1-[(1S,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oct-1-en-3-yl]but-3-enamide 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  手性烯丙基叠氮化物的空间偏向3,3-Sigmatropic重排：在生物碱的总合成中的应用

  摘要：

  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.

  DOI：

  10.1021/jo800817p
• 作为产物：
  描述：

  乙烯基乙酸 、 (E,3S)-7-[tert-butyl(dimethyl)silyl]oxy-1-[(1S,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oct-1-en-3-amine 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.75h， 以99%的产率得到N-[(E,3S)-7-[tert-butyl(dimethyl)silyl]oxy-1-[(1S,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oct-1-en-3-yl]but-3-enamide
  参考文献：
  名称：

  手性烯丙基叠氮化物的空间偏向3,3-Sigmatropic重排：在生物碱的总合成中的应用

  摘要：

  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.

  DOI：

  10.1021/jo800817p

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.