<4R-<4α(2E,4E),4aβ,7α(2S*,3E,5E),8β,8aβ>>-5-oxy>-3,5-heptadienyl>-4a,8-dimethyl-2,5-dioxo-2H,5H-pyrano<3,4-e>-1,3-oxazin-4-yl>-4-methyl-2,4-pentadienal | 152453-86-6

• 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: <4R-<4α(2E,4E),4aβ,7α(2S*,3E,5E),8β,8aβ>>-5-oxy>-3,5-heptadienyl>-4a,8-dimethyl-2,5-dioxo-2H,5H-pyrano<3,4-e>-1,3-oxazin-4-yl>-4-methyl-2,4-pentadienal
• 英文别名: (2E,4E)-5-[(4R,4aS,7R,8R,8aS)-7-[(2S,3E,5E)-2-[tert-butyl(dimethyl)silyl]oxy-7-chloro-5-methylhepta-3,5-dienyl]-4a,8-dimethyl-2,5-dioxo-4,7,8,8a-tetrahydro-3H-pyrano[3,4-e][1,3]oxazin-4-yl]-4-methylpenta-2,4-dienal
• CAS: 152453-86-6
• 化学式: C₂₉H₄₄ClNO₆Si
• 分子量: 566.21
• InChiKey: JOSRFNWHQKCZHX-UGKSESDXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.25
• 重原子数：
  38
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  90.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  <4R-<4α(2E,4E),4aβ,7α(2S*,3E,5E),8β,8aβ>>-5-oxy>-3,5-heptadienyl>-4a,8-dimethyl-2,5-dioxo-2H,5H-pyrano<3,4-e>-1,3-oxazin-4-yl>-4-methyl-2,4-pentadienal 在 咪唑 、 potassium cyanide 、 lithium hydroxide 、 sodium hydroxide 、 硼烷四氢呋喃络合物 、 18-冠醚-6 、 溶剂黄146 、 lithium hexamethyldisilazane 、 (R)-CBS 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 苯 为溶剂， 反应 4.91h， 生成 <2S-<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-oxopropanamide
  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：

  <4R-<4R*<αR*(S*),γS*>>>-γ-<(4-methoxyphenyl)methoxy>-2,2-dimethyl-α-(1-methyl-2-propenyl)-1,3-dioxolane-4-propanol 在 双(乙腈)氯化钯(II) 咪唑 、 2,6-二甲基吡啶 、 chromium dichloride 、 lead(IV) acetate 、 盐酸 、 lithium hydroxide 、 sodium chlorite 、 sodium dihydrogenphosphate 、 ammonium cerium(IV) nitrate 、 甲烷磺酸 、 二甲基硫 、 oil scarlet 、 四丁基氟化铵 、 氧气 、 三乙基氢硼化钾 、 戴斯-马丁氧化剂 、 臭氧 、 甲基磺酰氯 、 三乙胺 、 三苯基膦 、 lithium chloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 乙醚 、 二氯甲烷 、 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 111.17h， 生成 <4R-<4α(2E,4E),4aβ,7α(2S*,3E,5E),8β,8aβ>>-5-oxy>-3,5-heptadienyl>-4a,8-dimethyl-2,5-dioxo-2H,5H-pyrano<3,4-e>-1,3-oxazin-4-yl>-4-methyl-2,4-pentadienal
  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

• Enantioselective total synthesis of lankacidin C
  作者：Andrew S. Kende、Kevin Koch、Gilbert Dorey、Istvan Kaldor、Kun Liu

  DOI：10.1021/ja00074a078

  日期：1993.10
• 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).