Ethyl <2Z,4R,8R,9S,10S,13S,14S,17R,17<2S,3S,6R,8S,8(3S),9R>>-4-<oxy>-14-<(triethylsilyl)oxy>-10-hydroxy-9-methoxy-2,13,17-trimethyl-3-<(1,1-dimethylethoxy)carbonyl>-8-(1-methylethyl)-17-<3,9-dimethyl-8-... | 166239-70-9

• 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: Ethyl <2Z,4R,8R,9S,10S,13S,14S,17R,17<2S,3S,6R,8S,8(3S),9R>>-4-<oxy>-14-<(triethylsilyl)oxy>-10-hydroxy-9-methoxy-2,13,17-trimethyl-3-<(1,1-dimethylethoxy)carbonyl>-8-(1-methylethyl)-17-<3,9-dimethyl-8-...
• CAS: 166239-70-9
• 化学式: C₆₀H₁₁₀O₁₃Si₂
• 分子量: 1095.7
• InChiKey: NUCCMZABUMTVFD-HQWVQQOISA-N

物化性质

• 沸点：
  915.0±65.0 °C(predicted)
• 密度：
  1.03±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  13.65
• 重原子数：
  75.0
• 可旋转键数：
  33.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  162.35
• 氢给体数：
  1.0
• 氢受体数：
  13.0

反应信息

• 作为反应物：
  描述：

  Ethyl <2Z,4R,8R,9S,10S,13S,14S,17R,17<2S,3S,6R,8S,8(3S),9R>>-4-<oxy>-14-<(triethylsilyl)oxy>-10-hydroxy-9-methoxy-2,13,17-trimethyl-3-<(1,1-dimethylethoxy)carbonyl>-8-(1-methylethyl)-17-<3,9-dimethyl-8-... 在 氢氟酸 作用下， 以 乙腈 为溶剂， 反应 1.5h， 以100%的产率得到Ethyl <2Z,4R,8R,9S,10S,13S,14S,17R,17<2S,3S,6R,8S,8(3S),9R>>-4,10,14-trihydroxy-9-methoxy-2,13,17-trimethyl-3-<(1,1-dimethylethoxy)carbonyl>-8-(1-methylethyl)-17-<3,9-dimethyl-8-(3-methyl-4-pentenyl)-1,7-dioxaspiro<5.5>undec-2-yl>-6,12-dioxo-7-oxa...
  参考文献：
  名称：

  Total Synthesis of Tautomycin

  摘要：

  A convergent stereocontrolled synthesis of the antifungal antibiotic tautomycin, a potent protein phosphatases inhibitor, has been achieved first via key aldol coupling of two large subunits, a right-hand C-1-C-21 ketone and a left-hand aldehyde (left from C-22). The C-1-C-10 segment was synthesized through a remote stereochemical control process using a spiroketal template. After joining with the C-11-C-18 segment, the spiroketal moiety was selectively constructed. Then the right-hand C-1-C-21 ketone was synthesized via Roush asymmetric crotylboration. The left-hand aldehyde was prepared from a C-21-C-26 Segment and a dialkylmaleic anhydride segment. Completely stereoselective assemblage of the two subunits, the right-hand and the left-hand, was achieved by employing the Mukaiyama aldol reaction. Further functional group manipulations including desilylation, oxidation at C-2, and deprotection of tert-butyl ester with concomitant anhydride formation provided tautomycin which was identical with the natural product. As a preliminary study, derivatizations and degradation of the natural product were also examined to support the total synthesis.

  DOI：

  10.1021/jo00121a026
• 作为产物：
  描述：

  <2S,2(1R,4S,5S),3S,6R,8S,8(3S),9R>-2-<4-<(Triethylsilyl)oxy>-1,5-dimethyl-6-oxoheptyl>-3,9-dimethyl-8-(3-methyl-4-pentenyl)-1,7-dioxaspiro<5.5>undecane 、 (1R,2R)-1-Formyl-1-methoxy-3-methyl-2-butyl (4Z,3R)-5-(ethoxycarbonyl)-3-<oxy>-4-<(1,1-dimethylethoxy)carbonyl>-4-hexenoate 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 以30%的产率得到Ethyl <2Z,4R,8R,9S,10S,13S,14S,17R,17<2S,3S,6R,8S,8(3S),9R>>-4-<oxy>-14-<(triethylsilyl)oxy>-10-hydroxy-9-methoxy-2,13,17-trimethyl-3-<(1,1-dimethylethoxy)carbonyl>-8-(1-methylethyl)-17-<3,9-dimethyl-8-...
  参考文献：
  名称：

  Total Synthesis of Tautomycin

  摘要：

  A convergent stereocontrolled synthesis of the antifungal antibiotic tautomycin, a potent protein phosphatases inhibitor, has been achieved first via key aldol coupling of two large subunits, a right-hand C-1-C-21 ketone and a left-hand aldehyde (left from C-22). The C-1-C-10 segment was synthesized through a remote stereochemical control process using a spiroketal template. After joining with the C-11-C-18 segment, the spiroketal moiety was selectively constructed. Then the right-hand C-1-C-21 ketone was synthesized via Roush asymmetric crotylboration. The left-hand aldehyde was prepared from a C-21-C-26 Segment and a dialkylmaleic anhydride segment. Completely stereoselective assemblage of the two subunits, the right-hand and the left-hand, was achieved by employing the Mukaiyama aldol reaction. Further functional group manipulations including desilylation, oxidation at C-2, and deprotection of tert-butyl ester with concomitant anhydride formation provided tautomycin which was identical with the natural product. As a preliminary study, derivatizations and degradation of the natural product were also examined to support the total synthesis.

  DOI：

  10.1021/jo00121a026