<1S-(1R*,2S*,3E,5E,7R*,9E,11E,13R*,15S*,19S*)>-N-<18-hydroxy-7,13-bis<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1,4,10,19-tetramethyl-17-oxo-16-oxabicyclo<13.2.2>nonadeca-3,5,9,11-tetraen-2-yl>-2-hydroxypropanamide | 166185-91-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: <1S-(1R*,2S*,3E,5E,7R*,9E,11E,13R*,15S*,19S*)>-N-<18-hydroxy-7,13-bis<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1,4,10,19-tetramethyl-17-oxo-16-oxabicyclo<13.2.2>nonadeca-3,5,9,11-tetraen-2-yl>-2-hydroxypropanamide
• CAS: 166185-91-7
• 化学式: C₃₇H₆₃NO₇Si₂
• 分子量: 690.081
• InChiKey: BPVRQQZFEYUHAJ-IQJJLGHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.57
• 重原子数：
  47.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  111.16
• 氢给体数：
  2.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  <1S-(1R*,2S*,3E,5E,7R*,9E,11E,13R*,15S*,19S*)>-N-<18-hydroxy-7,13-bis<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1,4,10,19-tetramethyl-17-oxo-16-oxabicyclo<13.2.2>nonadeca-3,5,9,11-tetraen-2-yl>-2-hydroxypropanamide 在 lithium hydroxide 、 双氧水 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 10.5h， 生成 <1S,5R,6E,8E,10S,12E,14E,16S,18R,21S,22R>-N-<1,2-dioxopropyl>-7,12,21,22-tetramethyl-10,16-bis<<(1,1-dimethylethyl)dimethylsilyl>oxy>-3,20-dioxo-2,19,4-dioxaazatricyclo<16.3.1.0^5,21>docosa-6,8,12,14-tetraene
  参考文献：
  名称：

  Total Synthesis of the Macrolide Antitumor Antibiotic Lankacidin C

  摘要：

  The first total synthesis of natural (-)-lankacidin C (I) has been achieved by a convergent, enantioselective sequence starting from D-arabinose and L-aspartic acid, proceeding through the tricyclic carbamate 15 as an advanced relay intermediate. Specifically, the beta-lactam diene intermediate 41 is acylated by the thiopyridyl ester 34c. The resulting beta-ketolactam 42 is stereospecifically reduced by KEt(3)BH to carbinol 43, which on desilylation undergoes acid-catalyzed N --> O acyl migration to yield the delta-lactone 44. The derived iodo aldehyde 46 undergoes Stille coupling to give tetraene 54a, which upon Stork-Takahashi cyclization to ketone 56 and CBS reduction gives the key relay 15. N-acylation of the latter, and then regioselective carbamate scission followed by Dess-Martin oxidation, produces the target antibiotic (-)-lankacidin C (1).

  DOI：

  10.1021/ja00136a025
• 作为产物：
  描述：

  <1S-(1R*,2S*,3E,5E,7R*,9E,11E,13R*,15S*,19S*)>-N-<7,13-bis<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1,4,10,19-tetramethyl-17,18-dioxo-16-oxabicyclo<13.2.2>nonadeca-3,5,9,11-tetraen-2-yl>-2-oxopropanamide 在 咪唑 、 sodium tetrahydroborate 、 甲酸 作用下， 以 四氢呋喃 、 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.5h， 生成 <1S-(1R*,2S*,3E,5E,7R*,9E,11E,13R*,15S*,19S*)>-N-<18-hydroxy-7,13-bis<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1,4,10,19-tetramethyl-17-oxo-16-oxabicyclo<13.2.2>nonadeca-3,5,9,11-tetraen-2-yl>-2-hydroxypropanamide
  参考文献：
  名称：

  Total Synthesis of the Macrolide Antitumor Antibiotic Lankacidin C

  摘要：

  The first total synthesis of natural (-)-lankacidin C (I) has been achieved by a convergent, enantioselective sequence starting from D-arabinose and L-aspartic acid, proceeding through the tricyclic carbamate 15 as an advanced relay intermediate. Specifically, the beta-lactam diene intermediate 41 is acylated by the thiopyridyl ester 34c. The resulting beta-ketolactam 42 is stereospecifically reduced by KEt(3)BH to carbinol 43, which on desilylation undergoes acid-catalyzed N --> O acyl migration to yield the delta-lactone 44. The derived iodo aldehyde 46 undergoes Stille coupling to give tetraene 54a, which upon Stork-Takahashi cyclization to ketone 56 and CBS reduction gives the key relay 15. N-acylation of the latter, and then regioselective carbamate scission followed by Dess-Martin oxidation, produces the target antibiotic (-)-lankacidin C (1).

  DOI：

  10.1021/ja00136a025