(3R,4R)-1-(tert-Butyl-dimethyl-silanyl)-4-[(1E,3E)-5-(tert-butyl-dimethyl-silanyloxy)-2-methyl-penta-1,3-dienyl]-3-methyl-azetidin-2-one | 152453-81-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: (3R,4R)-1-(tert-Butyl-dimethyl-silanyl)-4-[(1E,3E)-5-(tert-butyl-dimethyl-silanyloxy)-2-methyl-penta-1,3-dienyl]-3-methyl-azetidin-2-one
• 英文别名: (3R,4R)-1-[tert-butyl(dimethyl)silyl]-4-[(1E,3E)-5-[tert-butyl(dimethyl)silyl]oxy-2-methylpenta-1,3-dienyl]-3-methylazetidin-2-one
• CAS: 152453-81-1
• 化学式: C₂₂H₄₃NO₂Si₂
• 分子量: 409.76
• InChiKey: VMOZETZWDFXDJY-WSDRRJGDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.36
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3R,4R)-1-(tert-Butyl-dimethyl-silanyl)-4-[(1E,3E)-5-(tert-butyl-dimethyl-silanyloxy)-2-methyl-penta-1,3-dienyl]-3-methyl-azetidin-2-one 在 双(乙腈)氯化钯(II) 咪唑 、 2,6-二甲基吡啶 、 盐酸 、 potassium cyanide 、 sodium hydroxide 、 硼烷四氢呋喃络合物 、 ammonium cerium(IV) nitrate 、 甲烷磺酸 、 18-冠醚-6 、 四丁基氟化铵 、 三乙基氢硼化钾 、 戴斯-马丁氧化剂 、 溶剂黄146 、 甲基磺酰氯 、 三乙胺 、 lithium chloride 、 lithium hexamethyldisilazane 、 lithium diisopropyl amide 、 (R)-CBS 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 、 苯 为溶剂， 反应 36.08h， 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：

  (E)-2-Methyl-3-((S)-4-oxo-azetidin-2-yl)-propenal 在 二异丁基氢化铝 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 1.0h， 生成 (3R,4R)-1-(tert-Butyl-dimethyl-silanyl)-4-[(1E,3E)-5-(tert-butyl-dimethyl-silanyloxy)-2-methyl-penta-1,3-dienyl]-3-methyl-azetidin-2-one
  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