tert-butyl (9R*,10S*,11E,13S)-13-(acetoxy)-9,10-epoxy-11-octadecenoate | 252910-08-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: tert-butyl (9R*,10S*,11E,13S)-13-(acetoxy)-9,10-epoxy-11-octadecenoate
• CAS: 252910-08-0
• 化学式: C₂₄H₄₂O₅
• 分子量: 410.594
• InChiKey: MFDQCNGBSVQNJE-XWSAGXMVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.89
• 重原子数：
  29.0
• 可旋转键数：
  15.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  65.13
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  tert-butyl (9R*,10S*,11E,13S)-13-(acetoxy)-9,10-epoxy-11-octadecenoate 在 N-甲基吡咯烷酮 、 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 52.0h， 生成 tert-butyl (9R*,10R*,11E,13S)-10-({5-(acetylamino)-6[(4-methyl-2-oxo-2H-chromen-7-yl)amino]-6-oxohexyl}amino)-9,13-dihydroxy-11-octadecenoate
  参考文献：
  名称：

  Reactivity of Lysine Moieties toward an Epoxyhydroxylinoleic Acid Derivative:  Aminolysis versus Hydrolysis

  摘要：

  Epoxyols are generally accepted as crucial intermediates in lipid oxidation. The reactivity of tert-butyl (9R*,10S*,11E,13S)-9,10-epoxy-13-hydroxy-11-octadecenoate (11a,b) toward lysine moieties is investigated, employing N-2-acetyllysine 4-methylcoumar-7-ylamide (12) as a model for protein-bound lysine. The prefixes R* and S* denote the relative configuration at the respective stereogenic centers. Independent synthesis and unequivocal structural characterization are reported for 11a,b, its precursors, and tert-butyl (9R*,10R*,11E,13S)-10-({5-(acetylamino)-6-[(4-methyl-2-oxo-2H-chromen-7-yl)amino]-6-oxohexyl}amino)-9,13-dihydroxy-11-octadecenoate (13a-d). Reactions of 11a,b and 12 in 1-methyl-2-pyrrolidone (MP) and MP/water mixtures at pH 7.4 and 37 degrees C for 56 days show formation of the aminols 13a-d to be favored by an increased water content. The same trend is observed for hydrolytic cleavage of 11a,b to tert-butyl (E)-9,10,13-trihydroxy-11-octadecenoate (14) and tert-butyl (E)-9,12,13-trihydroxy-10-octadecenoate (15). Under the given conditions, aminolysis proceeds via an S(N)2 substitution, in contrast with the S(N)1 process for hydrolysis. In the MP/water (8:2) incubation, 15.8% of 12 has been transformed to 13a-d and 10.5% of 11a,b hydrolyzed to the regioisomers 14 and 15 after 8 weeks, respectively. Aminolysis of alpha,beta-unsaturated epoxides by lysine moieties therefore is expected to be an important mode of interaction between proteins and lipid oxidation products.

  DOI：

  10.1021/jf990383o
• 作为产物：
  描述：

  tert-butyl (9Z,11E,13S)-13-(acetoxy)-9,11-octadecadienoate 在 间氯过氧苯甲酸 作用下， 以 乙醚 为溶剂， 反应 24.0h， 以77%的产率得到tert-butyl (9R*,10S*,11E,13S)-13-(acetoxy)-9,10-epoxy-11-octadecenoate
  参考文献：
  名称：

  Reactivity of Lysine Moieties toward an Epoxyhydroxylinoleic Acid Derivative:  Aminolysis versus Hydrolysis

  摘要：

  Epoxyols are generally accepted as crucial intermediates in lipid oxidation. The reactivity of tert-butyl (9R*,10S*,11E,13S)-9,10-epoxy-13-hydroxy-11-octadecenoate (11a,b) toward lysine moieties is investigated, employing N-2-acetyllysine 4-methylcoumar-7-ylamide (12) as a model for protein-bound lysine. The prefixes R* and S* denote the relative configuration at the respective stereogenic centers. Independent synthesis and unequivocal structural characterization are reported for 11a,b, its precursors, and tert-butyl (9R*,10R*,11E,13S)-10-({5-(acetylamino)-6-[(4-methyl-2-oxo-2H-chromen-7-yl)amino]-6-oxohexyl}amino)-9,13-dihydroxy-11-octadecenoate (13a-d). Reactions of 11a,b and 12 in 1-methyl-2-pyrrolidone (MP) and MP/water mixtures at pH 7.4 and 37 degrees C for 56 days show formation of the aminols 13a-d to be favored by an increased water content. The same trend is observed for hydrolytic cleavage of 11a,b to tert-butyl (E)-9,10,13-trihydroxy-11-octadecenoate (14) and tert-butyl (E)-9,12,13-trihydroxy-10-octadecenoate (15). Under the given conditions, aminolysis proceeds via an S(N)2 substitution, in contrast with the S(N)1 process for hydrolysis. In the MP/water (8:2) incubation, 15.8% of 12 has been transformed to 13a-d and 10.5% of 11a,b hydrolyzed to the regioisomers 14 and 15 after 8 weeks, respectively. Aminolysis of alpha,beta-unsaturated epoxides by lysine moieties therefore is expected to be an important mode of interaction between proteins and lipid oxidation products.

  DOI：

  10.1021/jf990383o