(-)-6-{[2S-(2R*,3R*,4R*,5R*,6S*,10S*),7E]-4,10-dihydroxy-6-methoxy-3,5,8-trimethyl-11-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-[(trimethylsilyl)oxy]-undec-7-enyl}-2,2-dimethyl-4H-1,3-dioxin-4-one | 1112362-11-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-6-{[2S-(2R*,3R*,4R*,5R*,6S*,10S*),7E]-4,10-dihydroxy-6-methoxy-3,5,8-trimethyl-11-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-[(trimethylsilyl)oxy]-undec-7-enyl}-2,2-dimethyl-4H-1,3-dioxin-4-one
• 英文别名: 6-[(E,2S,3S,4S,5S,6R,10R)-11-[tert-butyl(dimethyl)silyl]oxy-4,10-dihydroxy-6-methoxy-3,5,8-trimethyl-2-trimethylsilyloxyundec-7-enyl]-2,2-dimethyl-1,3-dioxin-4-one
• CAS: 1112362-11-4
• 化学式: C₃₀H₅₈O₈Si₂
• 分子量: 602.957
• InChiKey: SRXPZTMMHURQIL-NHCDEMAVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.16
• 重原子数：
  40
• 可旋转键数：
  16
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  104
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (-)-6-{[2S-(2R*,3R*,4R*,5R*,6S*,10S*),7E]-4,10-dihydroxy-6-methoxy-3,5,8-trimethyl-11-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-[(trimethylsilyl)oxy]-undec-7-enyl}-2,2-dimethyl-4H-1,3-dioxin-4-one 以 苯 为溶剂， 反应 12.0h， 以76%的产率得到(-)-[1S(1R*,5S*,9S*,10S*,11S*,12R*,13R*)7E]-1-hydroxy-9-methoxy-7,10,12-trimethyl-5-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-13-[(trimethylsilyl)oxy]-4,15-dioxabicyclo[9.3.1]pentadec-7-en-3-one
  参考文献：
  名称：

  通过酰基乙烯酮的双大内酯化/吡喃-半缩酮形成：在合成（-）-callipeltoside A和lyngbyaloside B模型系统中的应用。

  摘要：

  Thermal generation of acylketenes in diol-containing substrates results in dual macrocyclization/pyran-hemiketal formation. This transformation expands the scope of acylketene macrolactonizations and their application to the synthesis of complex macrolides. Triol and even tetrol substrates also have been closed in highly regioselective fashion. Additionally, the challenging macrolactonization of a tertiary alcohol was achieved.

  DOI：

  10.1002/anie.200804049
• 作为产物：
  描述：

  三甲基氯硅烷 、 (+)-6-{[2S-(2R*,3S*,4S*,5S*,6S*,10S*),7E]-2-hydroxy-6-methoxy-5,10-bis-[(4-methoxyphenyl)methoxy]-3,5,8-trimethyl-11-[[(1,1-dimethylethyl)dimethylsilyl]-oxy]-undec-7-enyl}-2,2-dimethyl-4H-1,3-dioxin-4-one 在 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.5h， 以78%的产率得到(-)-6-{[2S-(2R*,3R*,4R*,5R*,6S*,10S*),7E]-4,10-dihydroxy-6-methoxy-3,5,8-trimethyl-11-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-[(trimethylsilyl)oxy]-undec-7-enyl}-2,2-dimethyl-4H-1,3-dioxin-4-one
  参考文献：
  名称：

  (-)-Callipeltoside A的全合成

  摘要：

  (-)-callipeltoside A ( 1 )的全合成已经实现。核心大环是通过双重大环内酯化/吡喃半缩酮形成反应制成的，开发该反应是为了避免与 β-酮内酯底物形成酰基烯酮的可逆性质相关的问题。还描述了围绕闭环复分解 (RCM) 和中继闭环复分解 (RRCM) 反应的天然产物核心的初步方法。

  DOI：

  10.1021/jo101598y

文献信息

• Total Synthesis of (−)-Callipeltoside A
  作者：Thomas R. Hoye、Michael E. Danielson、Aaron E. May、Hongyu Zhao

  DOI：10.1021/jo101598y

  日期：2010.11.5

  has been achieved. The core macrocycle was made via a dual macrolactonization/pyran hemiketal formation reaction, developed to circumvent issues related to the reversible nature of acylketene formation from β-keto lactone substrates. Initial approaches to the core of the natural product that revolved around ring-closing metathesis (RCM) and relay ring-closing metathesis (RRCM) reactions are also described

  (-)-callipeltoside A ( 1 )的全合成已经实现。核心大环是通过双重大环内酯化/吡喃半缩酮形成反应制成的，开发该反应是为了避免与 β-酮内酯底物形成酰基烯酮的可逆性质相关的问题。还描述了围绕闭环复分解 (RCM) 和中继闭环复分解 (RRCM) 反应的天然产物核心的初步方法。
• Dual Macrolactonization/Pyran-Hemiketal Formation via Acylketenes: Applications to the Synthesis of (−)-Callipeltoside A and a Lyngbyaloside B Model System
  作者：Thomas R. Hoye、Michael E. Danielson、Aaron E. May、Hongyu Zhao

  DOI：10.1002/anie.200804049

  日期：2008.12.1

  Thermal generation of acylketenes in diol-containing substrates results in dual macrocyclization/pyran-hemiketal formation. This transformation expands the scope of acylketene macrolactonizations and their application to the synthesis of complex macrolides. Triol and even tetrol substrates also have been closed in highly regioselective fashion. Additionally, the challenging macrolactonization of a tertiary alcohol was achieved.