2,4-dideoxy-3-O-<(1,1-dimethylethyl)diphenylsilyl>-5-O-<(4-methoxyphenyl)methyl>-2-methyl-6,7-O-(1-methylethylidene)-D-allo-heptose | 166186-04-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,4-dideoxy-3-O-<(1,1-dimethylethyl)diphenylsilyl>-5-O-<(4-methoxyphenyl)methyl>-2-methyl-6,7-O-(1-methylethylidene)-D-allo-heptose
• 英文别名: (2R,3R,5S)-3-[tert-butyl(diphenyl)silyl]oxy-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-5-[(4-methoxyphenyl)methoxy]-2-methylpentanal
• CAS: 166186-04-5
• 化学式: C₃₅H₄₆O₆Si
• 分子量: 590.832
• InChiKey: IUDVPNMJCWWLPC-NEVPTIFISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  42.0
• 可旋转键数：
  13.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  63.22
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  2,4-dideoxy-3-O-<(1,1-dimethylethyl)diphenylsilyl>-5-O-<(4-methoxyphenyl)methyl>-2-methyl-6,7-O-(1-methylethylidene)-D-allo-heptose 在 sodium chlorite 、 sodium dihydrogenphosphate 作用下， 以 甲醇 、 乙醚 、 二甲基亚砜 、 乙腈 为溶剂， 反应 5.25h， 生成 methyl (2R,3R,5S,6R)-3-[tert-butyl(diphenyl)silyl]oxy-6,7-dihydroxy-5-[(4-methoxyphenyl)methoxy]-2-methylheptanoate
  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：

  (1'S,4R)-4-(3',3'-bisethylthio-1'-p-methoxybenzyloxypropyl)-2,2-dimethyl-1,3-dioxolane 在 咪唑 、 sodium hydroxide 、 二甲基硫 、 oil scarlet 、 三氟化硼乙醚 、 双氧水 、 氧气 、 臭氧 、 calcium carbonate 、 mercury dichloride 作用下， 以 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 50.33h， 生成 2,4-dideoxy-3-O-<(1,1-dimethylethyl)diphenylsilyl>-5-O-<(4-methoxyphenyl)methyl>-2-methyl-6,7-O-(1-methylethylidene)-D-allo-heptose
  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