benzyl N-[(3aR,8R,9R,9aR,9bR)-5-hydroxy-2,2,8-trimethyl-6-oxo-3a,4,8,9,9a,9b-hexahydro-[1,3]dioxolo[4,5-f]isochromen-9-yl]carbamate | 105928-74-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: benzyl N-[(3aR,8R,9R,9aR,9bR)-5-hydroxy-2,2,8-trimethyl-6-oxo-3a,4,8,9,9a,9b-hexahydro-[1,3]dioxolo[4,5-f]isochromen-9-yl]carbamate
• CAS: 105928-74-3
• 化学式: C₂₁H₂₅NO₇
• 分子量: 403.432
• InChiKey: BKDAXKBAUAYDGT-VZTCGREFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  103
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  benzyl N-[(3aR,8R,9R,9aR,9bR)-5-hydroxy-2,2,8-trimethyl-6-oxo-3a,4,8,9,9a,9b-hexahydro-[1,3]dioxolo[4,5-f]isochromen-9-yl]carbamate 在 ammonium hydroxide 、 四丁基氟化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 8.0h， 生成 (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：

  氯甲酸苄酯 在 4-甲基苯磺酸吡啶 三乙胺 作用下， 以 乙酸乙酯 、 丙酮 为溶剂， 反应 18.0h， 生成 benzyl N-[(3aR,8R,9R,9aR,9bR)-5-hydroxy-2,2,8-trimethyl-6-oxo-3a,4,8,9,9a,9b-hexahydro-[1,3]dioxolo[4,5-f]isochromen-9-yl]carbamate
  参考文献：
  名称：

  放线菌素的受控还原和氧化

  摘要：

  埃德曼降解反应已应用于硫酸肌动蛋白（2a），所得盐酸盐bd3被转化为碳苄基衍生物4。用各种还原剂处理后者并没有导致，相应的N-乙酰基衍生物bd7发生了反应。用硼氢化钠得到半缩醛，bd8和内酯bd9的混合物。尽管后者都经过了酸催化的脱水，但是通过用氯化氢甲醇处理可以获得非对映体糖苷bd12的混合物。用硫酸水溶液水解bd12，Swern氧化和皂化反应，然后重新生成放线肌醇系统bd5a。

  DOI：

  10.1016/0040-4020(86)80003-5

文献信息

• Synthesis of (-)-bactobolin from D-glucose and from (+)-actinobolin
  作者：Dale E. Ward、Yuanzhu Gai、Brian F. Kaller

  DOI：10.1016/s0040-4039(00)73216-3

  日期：1994.5

  preparation of (-)-16 from (+)-3 constitutes a formal enantiospecific synthesis of (-)-bactobolin from D-glucose. The key transformation involves the diastereoselective addition of LiCHCl2 to 7 in the presence of CeCl3. The synthesis of (+)-3 from (+)-actinobolin sulfate is reported and illustrates the conversion of (+)-actinobolin into (-)-bactobolin.

  由（+）- 3制备（-）- 16构成了由D-葡萄糖形式的（-）-bacbolbolin的正式对映体合成。密钥变换涉及非对映选择性加成LiCHCl的2至7中加入CeCl的存在3。已经报道了由（+）-肌动蛋白硫酸盐合成（+）- 3，并说明了（+）-肌动蛋白转化为（-）-细菌肌动蛋白。