tert-butyl ((E)-4-(1S,2S,4R)-4-(2-(2,2-dimethoxyethyl)-4-methyl-1-(triethylsilyloxy)cyclopentyl)-6-phenoxyhex-4-enyloxy)diphenylsilane | 1384122-51-3

• 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: tert-butyl ((E)-4-(1S,2S,4R)-4-(2-(2,2-dimethoxyethyl)-4-methyl-1-(triethylsilyloxy)cyclopentyl)-6-phenoxyhex-4-enyloxy)diphenylsilane
• 英文别名: tert-butyl-[(E)-4-[(1S,2S,4R)-2-(2,2-dimethoxyethyl)-4-methyl-1-triethylsilyloxycyclopentyl]-6-phenoxyhex-4-enoxy]-diphenylsilane
• CAS: 1384122-51-3
• 化学式: C₄₄H₆₆O₅Si₂
• 分子量: 731.176
• InChiKey: FSMXCKKNECIJBH-UGFYXODDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.16
• 重原子数：
  51
• 可旋转键数：
  21
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-butyl ((E)-4-(1S,2S,4R)-4-(2-(2,2-dimethoxyethyl)-4-methyl-1-(triethylsilyloxy)cyclopentyl)-6-phenoxyhex-4-enyloxy)diphenylsilane 在 四氯化钛 、 三乙胺 作用下， 以 二氯甲烷 、 甲醇 为溶剂， 反应 0.33h， 以37.5%的产率得到
  参考文献：
  名称：

  Total Synthesis of (+)-Sieboldine A: Evolution of a Pinacol-Terminated Cyclization Strategy

  摘要：

  This article describes synthetic studies that culminated in the first total synthesis of the Lycopodium alkaloid sieboldine A. During this study, a number of pinacol-terminated cationic cyclizations were examined to form the cis-hydrindanone core of sieboldine A. Of these, a mild Au(I)-promoted 1,6-enyne cyclization that was terminated by a semipinacol rearrangement proved to be most efficient. Fashioning the unprecedented N-hydroxyazacyclononane ring embedded within the bicyclo[5.2.1]decane-N,O-acetal moiety of sieboldine A was a formidable challenge. Ultimately, the enantioselective total synthesis of (+)-sieboldine A was completed by forming this ring in good yield by cyclization of a protected-hydroxylamine thioglycoside precursor.

  DOI：

  10.1021/jo300872y
• 作为产物：
  描述：

  Methyl 6-(tert-butyldiphenylsiloxy)-2-hexynoate 在 2,6-二甲基吡啶 、 草酰氯 、 copper(I) bromide dimethylsulfide complex 、 偶氮二甲酸二异丙酯 、 碘 、 仲丁基锂 、 4-甲基苯磺酸吡啶 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 17.75h， 生成 tert-butyl ((E)-4-(1S,2S,4R)-4-(2-(2,2-dimethoxyethyl)-4-methyl-1-(triethylsilyloxy)cyclopentyl)-6-phenoxyhex-4-enyloxy)diphenylsilane
  参考文献：
  名称：

  Total Synthesis of (+)-Sieboldine A: Evolution of a Pinacol-Terminated Cyclization Strategy

  摘要：

  This article describes synthetic studies that culminated in the first total synthesis of the Lycopodium alkaloid sieboldine A. During this study, a number of pinacol-terminated cationic cyclizations were examined to form the cis-hydrindanone core of sieboldine A. Of these, a mild Au(I)-promoted 1,6-enyne cyclization that was terminated by a semipinacol rearrangement proved to be most efficient. Fashioning the unprecedented N-hydroxyazacyclononane ring embedded within the bicyclo[5.2.1]decane-N,O-acetal moiety of sieboldine A was a formidable challenge. Ultimately, the enantioselective total synthesis of (+)-sieboldine A was completed by forming this ring in good yield by cyclization of a protected-hydroxylamine thioglycoside precursor.

  DOI：

  10.1021/jo300872y

文献信息

• Total Synthesis of (+)-Sieboldine A: Evolution of a Pinacol-Terminated Cyclization Strategy
  作者：Stephen M. Canham、David J. France、Larry E. Overman

  DOI：10.1021/jo300872y

  日期：2013.1.4

  This article describes synthetic studies that culminated in the first total synthesis of the Lycopodium alkaloid sieboldine A. During this study, a number of pinacol-terminated cationic cyclizations were examined to form the cis-hydrindanone core of sieboldine A. Of these, a mild Au(I)-promoted 1,6-enyne cyclization that was terminated by a semipinacol rearrangement proved to be most efficient. Fashioning the unprecedented N-hydroxyazacyclononane ring embedded within the bicyclo[5.2.1]decane-N,O-acetal moiety of sieboldine A was a formidable challenge. Ultimately, the enantioselective total synthesis of (+)-sieboldine A was completed by forming this ring in good yield by cyclization of a protected-hydroxylamine thioglycoside precursor.