(4R*)-Methyl 2-(N-benzoylamino)-4-(benzyloxy)-5-methyl-(2E)-hexenoate | 149287-52-5

• 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: (4R*)-Methyl 2-(N-benzoylamino)-4-(benzyloxy)-5-methyl-(2E)-hexenoate
• CAS: 149287-52-5
• 化学式: C₂₂H₂₅NO₄
• 分子量: 367.445
• InChiKey: IJRVGZJDWPXQKP-XMHGGMMESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.71
• 重原子数：
  27.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  64.63
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (4R*)-Methyl 2-(N-benzoylamino)-4-(benzyloxy)-5-methyl-(2E)-hexenoate 在 2,2,6,6-四甲基哌啶 、 N-溴代丁二酰亚胺(NBS) 作用下， 生成 (2Z,4R*)-Methyl 2-(N-benzoylamino)-4-(benzyloxy)-3-bromo-5-methyl-2-hexenoate 、 (2E,4R*)-Methyl 2-(N-benzoylamino)-4-(benzyloxy)-3-bromo-5-methyl-2-hexenoate
  参考文献：
  名称：

  Stereoselective bromination of dehydroamino acids with controllable retention or inversion of olefin configuration

  摘要：

  Dehydroamino acid esters react with brominating reagents to produce syn-a-bromo imines as the major products, which undergo tautomerization to mixtures of the diastereomeric (E)- and (Z)-beta-bromo-alpha,beta-dehydroamino acids upon treatment with base. Herein, we examine the characteristics of dehydroamino acid substrates 1 that affect both the diastereofacial selectivity of the bromination and the configuration of the resulting olefin product(s) 3. In these studies, we demonstrate E- and Z-diastereoselectivity for this reaction using kinetic and thermodynamic reaction conditions. Z-Vinyl bromides were shown to be the thermodynamically more stable products and were formed from the kinetic E-isomers by DABCO-induced isomerization. High levels of kinetic E-selectivity were obtained by treatment of the intermediate alpha-bromo imines with hindered amine bases such as 2,2,6,6-tetramethylpiperidine or sodium hexamethyldisilazide. The reaction conditions detailed herein allow for the stereodivergent preparation of both E- and Z-vinyl bromide products from either diastereomeric E- or Z-olefin starting material with useful levels of diastereoselectivity.

  DOI：

  10.1021/jo00068a047
• 作为产物：
  描述：

  2-羟基-3-甲基丁酸 在 lithium aluminium tetrahydride 、 草酰氯 、 四丁基碘化铵 、 sodium hydride 、 二甲基亚砜 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 6.75h， 生成 (4R*)-Methyl 2-(N-benzoylamino)-4-(benzyloxy)-5-methyl-(2E)-hexenoate
  参考文献：
  名称：

  Stereoselective bromination of dehydroamino acids with controllable retention or inversion of olefin configuration

  摘要：

  Dehydroamino acid esters react with brominating reagents to produce syn-a-bromo imines as the major products, which undergo tautomerization to mixtures of the diastereomeric (E)- and (Z)-beta-bromo-alpha,beta-dehydroamino acids upon treatment with base. Herein, we examine the characteristics of dehydroamino acid substrates 1 that affect both the diastereofacial selectivity of the bromination and the configuration of the resulting olefin product(s) 3. In these studies, we demonstrate E- and Z-diastereoselectivity for this reaction using kinetic and thermodynamic reaction conditions. Z-Vinyl bromides were shown to be the thermodynamically more stable products and were formed from the kinetic E-isomers by DABCO-induced isomerization. High levels of kinetic E-selectivity were obtained by treatment of the intermediate alpha-bromo imines with hindered amine bases such as 2,2,6,6-tetramethylpiperidine or sodium hexamethyldisilazide. The reaction conditions detailed herein allow for the stereodivergent preparation of both E- and Z-vinyl bromide products from either diastereomeric E- or Z-olefin starting material with useful levels of diastereoselectivity.

  DOI：

  10.1021/jo00068a047