Isopropyl 2-hydroxy-5-methyl-4-methylene-5-hexenoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Isopropyl 2-hydroxy-5-methyl-4-methylene-5-hexenoate
• 英文别名: Propan-2-yl 2-hydroxy-5-methyl-4-methylidenehex-5-enoate
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: ADDMLQMLUFTQOW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  isopropyl glyoxalate 、 2,3-二甲基-1,3-丁二烯 在 copper(II) bis(trifluoromethanesulfonate) 、 (R,R)-2,2'-异亚丙基双(4-苯基-2-恶唑啉) 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 生成 Isopropyl 2-hydroxy-5-methyl-4-methylene-5-hexenoate 、 (R)-(+)-isopropyl 4,5-dimethyl-3,6-dihydro-2H-pyran-2-carboxylate 、 (S)-Isopropyl 4,5-dimethyl-3,6-dihydro-2H-pyran-2-carboxylate
  参考文献：
  名称：

  Asymmetric hetero Diels-Alder reactions and ene reactions catalyzed by chiral copper(II) complexes

  摘要：

  A new copper(II) bisoxazoline-catalyzed reaction of glyoxylate esters with dienes leading to the hetero Diet-Alder product and the ene product in high yield and with a high enantiomeric excess (ee) has been developed. The hetero Diels-Alder product:ene product ratio is in the range 1:0.6 to 1:1.8 and is dependent on both the chiral ligand attached to the metal, the glyoxylate ester, and the reaction temperature. The scope of the copper(II) bisoxazoline-catalyzed reaction of glyoxylate esters with dienes is demonstrated by the reaction of a variety of different dienes with ethyl and isopropyl glyoxylate, and it is shown that a simple substrate such as 1,3-butadiene reacts to give the hetero Diels-Alder product in 55% yield with an ee of 87%. Furthermore, the synthetic application of the reaction is demonstrated by the synthesis of a highly interesting synthon for sesquiterpene lactones in high yield and diastereoselectivity, and with a very high ee from 1,3-cyclohexadiene and ethyl glyoxylate using a copper(II) bisoxazoline as the catalyst. A mechanism for the hetero Diels-Alder reaction, which accounts for the enantioselectivity in the reactions, is proposed.

  DOI：

  10.1021/jo00123a007

文献信息

• Asymmetric hetero Diels-Alder reactions and ene reactions catalyzed by chiral copper(II) complexes
  作者：Mogens Johannsen、Karl Anker Joergensen

  DOI：10.1021/jo00123a007

  日期：1995.9

  A new copper(II) bisoxazoline-catalyzed reaction of glyoxylate esters with dienes leading to the hetero Diet-Alder product and the ene product in high yield and with a high enantiomeric excess (ee) has been developed. The hetero Diels-Alder product:ene product ratio is in the range 1:0.6 to 1:1.8 and is dependent on both the chiral ligand attached to the metal, the glyoxylate ester, and the reaction temperature. The scope of the copper(II) bisoxazoline-catalyzed reaction of glyoxylate esters with dienes is demonstrated by the reaction of a variety of different dienes with ethyl and isopropyl glyoxylate, and it is shown that a simple substrate such as 1,3-butadiene reacts to give the hetero Diels-Alder product in 55% yield with an ee of 87%. Furthermore, the synthetic application of the reaction is demonstrated by the synthesis of a highly interesting synthon for sesquiterpene lactones in high yield and diastereoselectivity, and with a very high ee from 1,3-cyclohexadiene and ethyl glyoxylate using a copper(II) bisoxazoline as the catalyst. A mechanism for the hetero Diels-Alder reaction, which accounts for the enantioselectivity in the reactions, is proposed.