N-[(3R,4R,4aR,5R,6R)-5,6-dihydroxy-8-methoxy-3-methyl-1-oxo-3,4,4a,5,6,7-hexahydroisochromen-4-yl]-2-trimethylsilylethanesulfonamide | 180512-30-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: N-[(3R,4R,4aR,5R,6R)-5,6-dihydroxy-8-methoxy-3-methyl-1-oxo-3,4,4a,5,6,7-hexahydroisochromen-4-yl]-2-trimethylsilylethanesulfonamide
• CAS: 180512-30-5
• 化学式: C₁₆H₂₉NO₇SSi
• 分子量: 407.56
• InChiKey: IJKHPWVQTHSORP-PSDLAXTLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  131
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  N-[(3R,4R,4aR,5R,6R)-5,6-dihydroxy-8-methoxy-3-methyl-1-oxo-3,4,4a,5,6,7-hexahydroisochromen-4-yl]-2-trimethylsilylethanesulfonamide 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成 (3R,3aR,4R,5R)-4,5-Dihydroxy-3-((R)-1-hydroxy-ethyl)-7-methoxy-2,3,3a,4,5,7a-hexahydro-isoindol-1-one 、 (3R,3aR,4R,5R)-4,5-Dihydroxy-3-((R)-1-hydroxy-ethyl)-7-methoxy-2,3,3a,4,5,6-hexahydro-isoindol-1-one
  参考文献：
  名称：

  Synthetic Studies on Actinobolin and Bactobolin:  Synthesis of N-Desalanyl-N-[2-(trimethylsilyl)ethanesulfonyl] Derivatives from a Common Intermediate and Attempted Removal of the SES Protecting Group

  摘要：

  Two closely related syntheses of 5,6-O-(2-propylidene)-N-desalanyl-N-2-(trimethylsilyl)ethane-sulfonyl]bactobolin (9b) from (+)-12, an intermediate previously prepared from D-glucose, are reported. In each case, the key step involves a precedented stereoselective addition of LiCHCl2 in the presence of CeCl3 to a suitably protected a-amino ketone, Intermediates from both synthetic routes to 9b can be prepared by degradation of actinobolin (2) thereby establishing a potential method for the transformation of actinobolin into bactobolin. An efficient route to 5,6-O-(2-propylidene)-N-desalanyl-N-[[2-(trimethylsily)ethanesulfonyl]actinbolin (7b) from (+)-12 involving an unexpected cyclization of 29 was discovered. The 2-(trimethylsilyl)ethanesulfonyl (SES) protecting group in 7b tvas removed by reaction with Bu(4)NF in wet THF. The nature of the Bu(4)NF reagent was found to be important to the outcome of the reaction. Several improvements over our previously reported synthesis of actinobolin from D-glucose are noted. Although precedented, the removal of the SES protecting group from 9b could not be achieved thereby preventing completion of a total synthesis of bactobolin.

  DOI：

  10.1021/jo960579c
• 作为产物：
  描述：

  2-(三甲基硅基)乙烷磺酰氯 在 吡啶 、 正丁基锂 、 1,10-菲罗啉 、 二甲基硫 、 sodium methylate 、 sodium hydride 、 臭氧 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 反应 47.0h， 生成 N-[(3R,4R,4aR,5R,6R)-5,6-dihydroxy-8-methoxy-3-methyl-1-oxo-3,4,4a,5,6,7-hexahydroisochromen-4-yl]-2-trimethylsilylethanesulfonamide
  参考文献：
  名称：

  Synthetic Studies on Actinobolin and Bactobolin:  Synthesis of N-Desalanyl-N-[2-(trimethylsilyl)ethanesulfonyl] Derivatives from a Common Intermediate and Attempted Removal of the SES Protecting Group

  摘要：

  Two closely related syntheses of 5,6-O-(2-propylidene)-N-desalanyl-N-2-(trimethylsilyl)ethane-sulfonyl]bactobolin (9b) from (+)-12, an intermediate previously prepared from D-glucose, are reported. In each case, the key step involves a precedented stereoselective addition of LiCHCl2 in the presence of CeCl3 to a suitably protected a-amino ketone, Intermediates from both synthetic routes to 9b can be prepared by degradation of actinobolin (2) thereby establishing a potential method for the transformation of actinobolin into bactobolin. An efficient route to 5,6-O-(2-propylidene)-N-desalanyl-N-[[2-(trimethylsily)ethanesulfonyl]actinbolin (7b) from (+)-12 involving an unexpected cyclization of 29 was discovered. The 2-(trimethylsilyl)ethanesulfonyl (SES) protecting group in 7b tvas removed by reaction with Bu(4)NF in wet THF. The nature of the Bu(4)NF reagent was found to be important to the outcome of the reaction. Several improvements over our previously reported synthesis of actinobolin from D-glucose are noted. Although precedented, the removal of the SES protecting group from 9b could not be achieved thereby preventing completion of a total synthesis of bactobolin.

  DOI：

  10.1021/jo960579c