(E)-2-Methyl-3-((S)-4-oxo-azetidin-2-yl)-propenal | 166186-06-7

• 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: (E)-2-Methyl-3-((S)-4-oxo-azetidin-2-yl)-propenal
• 英文别名: (E)-2-methyl-3-[(2S)-4-oxoazetidin-2-yl]prop-2-enal
• CAS: 166186-06-7
• 化学式: C₇H₉NO₂
• 分子量: 139.154
• InChiKey: QHCZNLDEHHTGIE-AOPYWJJESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  46.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-2-Methyl-3-((S)-4-oxo-azetidin-2-yl)-propenal 在 双(乙腈)氯化钯(II) 咪唑 、 2,6-二甲基吡啶 、 盐酸 、 potassium cyanide 、 lithium hydroxide 、 sodium hydroxide 、 sodium tetrahydroborate 、 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 、 二异丁基氢化铝 、 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 、 甲醇 、 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 38.83h， 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
• 作为产物：
  描述：

  (4S,1'E)-4-(3'-hydroxy-2'-methylprop-1'-enyl)azetidin-2-one 在 草酰氯 、 二甲基亚砜 作用下， 以 二氯甲烷 为溶剂， 以86%的产率得到(E)-2-Methyl-3-((S)-4-oxo-azetidin-2-yl)-propenal
  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

文献信息

• Total Synthesis of the Macrolide Antitumor Antibiotic Lankacidin C
  作者：Andrew S. Kende、Kun Liu、Istvan Kaldor、Gilbert Dorey、Kevin Koch

  DOI：10.1021/ja00136a025

  日期：1995.8

  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).