methyl (1R,6R,7R,7aR)-7a-[[(1,1-dimethylethyl)dimethylsilyl]oxy]hexahydro-5-oxo-6,7-bis[(trimethylsilyl)oxy]-1H-pyrrolizine-1-carboxylate | 877309-46-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯里西啶类
• 英文名称: methyl (1R,6R,7R,7aR)-7a-[[(1,1-dimethylethyl)dimethylsilyl]oxy]hexahydro-5-oxo-6,7-bis[(trimethylsilyl)oxy]-1H-pyrrolizine-1-carboxylate
• 英文别名: methyl (1R,6R,7R,7aR)-7a-(tert-butyldimethylsilyloxy)-5-oxo-6,7-bis(trimethylsilyloxy)-hexahydro-1H-pyrrolizine-1-carboxylate；methyl (1R,6R,7R,8R)-8-[tert-butyl(dimethyl)silyl]oxy-5-oxo-6,7-bis(trimethylsilyloxy)-2,3,6,7-tetrahydro-1H-pyrrolizine-1-carboxylate
• CAS: 877309-46-1
• 化学式: C₂₁H₄₃NO₆Si₃
• 分子量: 489.832
• InChiKey: MMCMLHQLEVUZJU-BIZBXSGISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.18
• 重原子数：
  31
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  74.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (1R,6R,7R,7aR)-7a-[[(1,1-dimethylethyl)dimethylsilyl]oxy]hexahydro-5-oxo-6,7-bis[(trimethylsilyl)oxy]-1H-pyrrolizine-1-carboxylate 在 盐酸 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以42%的产率得到methyl (1R,6R,7R,7aR)-7a-[[(1,1-dimethylethyl)dimethylsilyl]oxy]hexahydro-5-oxo-6,7-dihydroxy-1H-pyrrolizine-1-carboxylate
  参考文献：
  名称：

  Silylative Dieckmann-Like Cyclizations of Ester-Imides (and Diesters)

  摘要：

  Trialkylsilyl triflates effect cyclization of ester-imides such as 2 to produce adducts such as 4a. Trapping of the in situ generated, nucleophilic ketene acetal (cf. 5a) is a key aspect of the transformation. A range of substrates amenable to this operationally simple reaction is reported. In many instances the levels of diastereoselectivity are very high. Mechanistic points are inferred from spectroscopic observations.

  DOI：

  10.1021/ol061988q
• 作为产物：
  描述：

  4-氨基丁酸甲酯盐酸盐 在 甲醇 、 二乙胺 、 三乙胺 、 N,N-二异丙基乙胺 、 乙酰氯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 48.58h， 生成 methyl (1R,6R,7R,7aR)-7a-[[(1,1-dimethylethyl)dimethylsilyl]oxy]hexahydro-5-oxo-6,7-bis[(trimethylsilyl)oxy]-1H-pyrrolizine-1-carboxylate
  参考文献：
  名称：

  Total Synthesis of UCS1025A

  摘要：

  The enantioselective total synthesis of the telomerase inhibitor UCS1025A has been accomplished. The key transformation involves a remarkable boron Reformatsky coupling of iodolactone 13 and aldehyde 17.

  DOI：

  10.1021/ja0574567

文献信息

• Silylative Dieckmann-Like Cyclizations of Ester-Imides (and Diesters)
  作者：Thomas R. Hoye、Vadims Dvornikovs、Elena Sizova

  DOI：10.1021/ol061988q

  日期：2006.11.9

  Trialkylsilyl triflates effect cyclization of ester-imides such as 2 to produce adducts such as 4a. Trapping of the in situ generated, nucleophilic ketene acetal (cf. 5a) is a key aspect of the transformation. A range of substrates amenable to this operationally simple reaction is reported. In many instances the levels of diastereoselectivity are very high. Mechanistic points are inferred from spectroscopic observations.
• Total Synthesis of UCS1025A
  作者：Tristan H. Lambert、Samuel J. Danishefsky

  DOI：10.1021/ja0574567

  日期：2006.1.1

  The enantioselective total synthesis of the telomerase inhibitor UCS1025A has been accomplished. The key transformation involves a remarkable boron Reformatsky coupling of iodolactone 13 and aldehyde 17.