[(1'S,4S,5'S,6'R,10'S,11'S,12'S,13'R)-13'-hydroxy-2,2,11',15',18',18'-hexamethyl-3'-oxo-10'-phenylmethoxyspiro[1,3-dioxolane-4,7'-2,4-dioxatetracyclo[12.3.1.01,5.06,11]octadeca-8,14-diene]-12'-yl] (1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carboxylate | 155899-03-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: [(1'S,4S,5'S,6'R,10'S,11'S,12'S,13'R)-13'-hydroxy-2,2,11',15',18',18'-hexamethyl-3'-oxo-10'-phenylmethoxyspiro[1,3-dioxolane-4,7'-2,4-dioxatetracyclo[12.3.1.01,5.06,11]octadeca-8,14-diene]-12'-yl] (1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carboxylate
• CAS: 155899-03-9
• 化学式: C₄₁H₅₂O₁₁
• 分子量: 720.857
• InChiKey: GWVLQEOZCPFSMX-JBVNPRMFSA-N

物化性质

• 沸点：
  805.4±65.0 °C(predicted)
• 密度：
  1.31±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  52
• 可旋转键数：
  6
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  136
• 氢给体数：
  1
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  [(1'S,4S,5'S,6'R,10'S,11'S,12'S,13'R)-13'-hydroxy-2,2,11',15',18',18'-hexamethyl-3'-oxo-10'-phenylmethoxyspiro[1,3-dioxolane-4,7'-2,4-dioxatetracyclo[12.3.1.01,5.06,11]octadeca-8,14-diene]-12'-yl] (1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carboxylate 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 0.5h， 以90%的产率得到(1'S,4S,5'S,6'R,10'S,11'R,12'S,13'R)-12',13'-dihydroxy-2,2,11',15',18',18'-hexamethyl-10'-phenylmethoxyspiro[1,3-dioxolane-4,7'-2,4-dioxatetracyclo[12.3.1.01,5.06,11]octadeca-8,14-diene]-3'-one
  参考文献：
  名称：

  Total Synthesis of Taxol. 3. Formation of Taxol's ABC Ring Skeleton

  摘要：

  The synthesis of Taxol's ABC ring system has been achieved. The Shapiro coupling of an aldehydic C ring synthon (8) with an anionic A ring synthon derived from hydrazone 9 gave, diastereoselectively, A-B conjugate 10. Functional group manipulations and McMurry ring closure produced the highly functionalized ABC ring system 17. Extensive attempts to optimize the McMurry reaction revealed a single predominant side reaction leading to byproducts 19 and 20. Resolution of the CB,C10-diol (+/-)-17 via its camphanyl esters provided the ABC ring system as its natural isomer (+)17.

  DOI：

  10.1021/ja00107a008
• 作为产物：
  描述：

  (4R,5R,5'R,6'S,7'S,8'R)-8'-Benzyloxy-7-(tert-butyl-dimethyl-silanyloxymethyl)-7'-(tert-butyl-diphenyl-silanyloxymethyl)-6,6,8,2',2',7'-hexamethyl-[4,6']bi[1,3-dioxa-spiro[4.5]decyl]-7,9'-dien-2-one 在 4-二甲氨基吡啶 、 四丙基高钌酸铵 、 TiCl₃-1,2-dimethoxyethane 、 4 A molecular sieve 、 四丁基氟化铵 、 铜 、 N-甲基吗啉氧化物 、 三乙胺 、 锌 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 二氯甲烷 、 乙腈 为溶剂， 反应 17.5h， 生成 [(1'S,4S,5'S,6'R,10'S,11'S,12'S,13'R)-13'-hydroxy-2,2,11',15',18',18'-hexamethyl-3'-oxo-10'-phenylmethoxyspiro[1,3-dioxolane-4,7'-2,4-dioxatetracyclo[12.3.1.01,5.06,11]octadeca-8,14-diene]-12'-yl] (1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carboxylate
  参考文献：
  名称：

  Total Synthesis of Taxol. 3. Formation of Taxol's ABC Ring Skeleton

  摘要：

  The synthesis of Taxol's ABC ring system has been achieved. The Shapiro coupling of an aldehydic C ring synthon (8) with an anionic A ring synthon derived from hydrazone 9 gave, diastereoselectively, A-B conjugate 10. Functional group manipulations and McMurry ring closure produced the highly functionalized ABC ring system 17. Extensive attempts to optimize the McMurry reaction revealed a single predominant side reaction leading to byproducts 19 and 20. Resolution of the CB,C10-diol (+/-)-17 via its camphanyl esters provided the ABC ring system as its natural isomer (+)17.

  DOI：

  10.1021/ja00107a008