(S)-2-{(2R,5R)-5-[(S)-2-(tert-Butyl-diphenyl-silanyloxy)-propyl]-tetrahydro-furan-2-yl}-1-((1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3λ⁶-thia-4-aza-tricyclo[5.2.1.0^1,5]dec-4-yl)-propan-1-one | 175273-62-8

• 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: (S)-2-{(2R,5R)-5-[(S)-2-(tert-Butyl-diphenyl-silanyloxy)-propyl]-tetrahydro-furan-2-yl}-1-((1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3λ⁶-thia-4-aza-tricyclo[5.2.1.0^1,5]dec-4-yl)-propan-1-one
• 英文别名: (2S)-2-[(2R,5R)-5-[(2S)-2-[tert-butyl(diphenyl)silyl]oxypropyl]oxolan-2-yl]-1-[(1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3lambda6-thia-4-azatricyclo[5.2.1.01,5]decan-4-yl]propan-1-one；(2S)-2-[(2R,5R)-5-[(2S)-2-[tert-butyl(diphenyl)silyl]oxypropyl]oxolan-2-yl]-1-[(1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3λ6-thia-4-azatricyclo[5.2.1.01,5]decan-4-yl]propan-1-one
• CAS: 175273-62-8
• 化学式: C₃₆H₅₁NO₅SSi
• 分子量: 637.956
• InChiKey: PDNGKISFAAUORT-YGDKSDDRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.89
• 重原子数：
  44
• 可旋转键数：
  9
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  81.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (S)-2-{(2R,5R)-5-[(S)-2-(tert-Butyl-diphenyl-silanyloxy)-propyl]-tetrahydro-furan-2-yl}-1-((1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3λ⁶-thia-4-aza-tricyclo[5.2.1.0^1,5]dec-4-yl)-propan-1-one 在 lithium hydroxide 、 双氧水 作用下， 以 四氢呋喃 为溶剂， 反应 10.0h， 生成 (S)-2-{(2R,5R)-5-[(S)-2-(tert-Butyl-diphenyl-silanyloxy)-propyl]-tetrahydro-furan-2-yl}-propionic acid
  参考文献：
  名称：

  Remote Allylic Silyloxy Groups as Stereocontrol Elements in Intramolecular Oxymercurations of γ-Hydroxyalkenes

  摘要：

  The diastereoselectivity in intramolecular oxymercurations of gamma-hydroxyalkenes bearing a remote allylic oxy substituent has been investigated, It was found that the best selectivity was obtained by employing a combination of (Z)-alkene geometry and a tert-butyldiphenylsilyl protecting group attached to the remote allylic oxygen as in 4a-g. Cyclization, using mercuric acetate in dichloromethane, of all the (Z)-alkenols gave the syn, diastereomer, 5a-g, as the major product. For example, cyclization of 4b gave syn diastereomer 5b and anti diastereomer 6b in a ratio of 7:1. It was found that this ratio could be improved by replacing dichloromethane with acetonitrile. Under these conditions the ratio of 5b to 6b increased to 19:1. Cyclization of (E)-alkene 9 gave very poor diastereoselection. These syn-selective intramolecular oxymercurations were exploited in enantioselective syntheses of two diastereomers of methyl nonactate.

  DOI：

  10.1021/jo951853q
• 作为产物：
  描述：

  [(1S,2S)-2-[tert-butyl(diphenyl)silyl]oxy-1-[(2R,5R)-5-[(2S)-1-[(1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3lambda6-thia-4-azatricyclo[5.2.1.01,5]decan-4-yl]-1-oxopropan-2-yl]oxolan-2-yl]propyl]-chloromercury 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 以99%的产率得到(S)-2-{(2R,5R)-5-[(S)-2-(tert-Butyl-diphenyl-silanyloxy)-propyl]-tetrahydro-furan-2-yl}-1-((1R,5S,7S)-10,10-dimethyl-3,3-dioxo-3λ⁶-thia-4-aza-tricyclo[5.2.1.0^1,5]dec-4-yl)-propan-1-one
  参考文献：
  名称：

  Remote Allylic Silyloxy Groups as Stereocontrol Elements in Intramolecular Oxymercurations of γ-Hydroxyalkenes

  摘要：

  The diastereoselectivity in intramolecular oxymercurations of gamma-hydroxyalkenes bearing a remote allylic oxy substituent has been investigated, It was found that the best selectivity was obtained by employing a combination of (Z)-alkene geometry and a tert-butyldiphenylsilyl protecting group attached to the remote allylic oxygen as in 4a-g. Cyclization, using mercuric acetate in dichloromethane, of all the (Z)-alkenols gave the syn, diastereomer, 5a-g, as the major product. For example, cyclization of 4b gave syn diastereomer 5b and anti diastereomer 6b in a ratio of 7:1. It was found that this ratio could be improved by replacing dichloromethane with acetonitrile. Under these conditions the ratio of 5b to 6b increased to 19:1. Cyclization of (E)-alkene 9 gave very poor diastereoselection. These syn-selective intramolecular oxymercurations were exploited in enantioselective syntheses of two diastereomers of methyl nonactate.

  DOI：

  10.1021/jo951853q