Dimethyl (2E,6E)-3-Methyl-2,6-octadienedioate | 141045-82-1

• 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: Dimethyl (2E,6E)-3-Methyl-2,6-octadienedioate
• 英文别名: dimethyl (2E,6E)-3-methylocta-2,6-dienedioate
• CAS: 141045-82-1
• 化学式: C₁₁H₁₆O₄
• 分子量: 212.246
• InChiKey: ZRNGJQHOHPHVRY-ZIRGRKGMSA-N

物化性质

• 沸点：
  299.9±40.0 °C(Predicted)
• 密度：
  1.039±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  lithium N-benzyltrimethylsilylamide 、 Dimethyl (2E,6E)-3-Methyl-2,6-octadienedioate 在 盐酸 作用下， 生成 Methyl (2S*)-3-(N-Benzylamino)-(2S*)-2-(methoxycarbonyl)-(1R*)-1-methylcyclopentaneacetate
  参考文献：
  名称：

  New type of cyclization of .alpha.,.beta.,.chi.,.psi.-unsaturated dioic acid esters through tandem conjugate additions by using lithium N-benzyl-N-(trimethylsilyl)amide as a nitrogen nucleophile

  摘要：

  Treatment of dimethyl (2E,6E)-2,6-octadienedioate with lithium N-benzyl-N-(trimethylsilyl)amide (LSA) gave 5-exo-trig ring closure products, methyl 3-(N-benzylamino)-2-(methoxycarbonyl)cyclopentane-1-acetates, through tandem conjugate additions. The related 6-exo-trig cyclization proceeded stereoselectively to give ethyl c-3-(N-benzylamino)-t-2-(ethoxycarbonyl)cyclohexane-1-acetate. In contrast with the 5- and 6-exo-trig cyclization, no 7-exo-trig cyclization occurred. The 5-exo-trig cyclization products were converted into 2-(methoxycarbonyl)-2-cyclopentene-1-carboxylic acid methyl ester in an excellent yield. 5-exo-trig cyclization of the unsymmetrical dienedioate consisting of crotonate and (E)-2-methyl-2-butenoate units proceeded regioselectively through conjugate addition of LSA to the crotonate part. Similar regioselectively was observed in the case of 5-exo-trig cyclization of the dienedioate possessing crotonate and (E)-3-methyl-2-pentenoate units. Total syntheses of the physiologically active cyclopentane monoterpenes (+/-)-dihydronepetalactone and (+/-)-isohydronepetalactone has been accomplished by this cyclization strategy. In addition, it has been demonstrated that LSA is a more efficient nitrogen nucleophile than LDA to cyclize omega-halo-alpha,beta-unsaturated esters.

  DOI：

  10.1021/jo00037a034
• 作为产物：
  描述：

  Methyl 3-Methyl-6-oxo-2-hexenoate 、 甲氧羰基亚甲基三苯基正膦 以 苯 为溶剂， 反应 18.0h， 生成 Dimethyl (2E,6E)-3-Methyl-2,6-octadienedioate
  参考文献：
  名称：

  New type of cyclization of .alpha.,.beta.,.chi.,.psi.-unsaturated dioic acid esters through tandem conjugate additions by using lithium N-benzyl-N-(trimethylsilyl)amide as a nitrogen nucleophile

  摘要：

  Treatment of dimethyl (2E,6E)-2,6-octadienedioate with lithium N-benzyl-N-(trimethylsilyl)amide (LSA) gave 5-exo-trig ring closure products, methyl 3-(N-benzylamino)-2-(methoxycarbonyl)cyclopentane-1-acetates, through tandem conjugate additions. The related 6-exo-trig cyclization proceeded stereoselectively to give ethyl c-3-(N-benzylamino)-t-2-(ethoxycarbonyl)cyclohexane-1-acetate. In contrast with the 5- and 6-exo-trig cyclization, no 7-exo-trig cyclization occurred. The 5-exo-trig cyclization products were converted into 2-(methoxycarbonyl)-2-cyclopentene-1-carboxylic acid methyl ester in an excellent yield. 5-exo-trig cyclization of the unsymmetrical dienedioate consisting of crotonate and (E)-2-methyl-2-butenoate units proceeded regioselectively through conjugate addition of LSA to the crotonate part. Similar regioselectively was observed in the case of 5-exo-trig cyclization of the dienedioate possessing crotonate and (E)-3-methyl-2-pentenoate units. Total syntheses of the physiologically active cyclopentane monoterpenes (+/-)-dihydronepetalactone and (+/-)-isohydronepetalactone has been accomplished by this cyclization strategy. In addition, it has been demonstrated that LSA is a more efficient nitrogen nucleophile than LDA to cyclize omega-halo-alpha,beta-unsaturated esters.

  DOI：

  10.1021/jo00037a034

文献信息

• New type of cyclization of .alpha.,.beta.,.chi.,.psi.-unsaturated dioic acid esters through tandem conjugate additions by using lithium N-benzyl-N-(trimethylsilyl)amide as a nitrogen nucleophile
  作者：Tadao Uyehara、Naomi Shida、Yoshinori Yamamoto

  DOI：10.1021/jo00037a034

  日期：1992.5

  Treatment of dimethyl (2E,6E)-2,6-octadienedioate with lithium N-benzyl-N-(trimethylsilyl)amide (LSA) gave 5-exo-trig ring closure products, methyl 3-(N-benzylamino)-2-(methoxycarbonyl)cyclopentane-1-acetates, through tandem conjugate additions. The related 6-exo-trig cyclization proceeded stereoselectively to give ethyl c-3-(N-benzylamino)-t-2-(ethoxycarbonyl)cyclohexane-1-acetate. In contrast with the 5- and 6-exo-trig cyclization, no 7-exo-trig cyclization occurred. The 5-exo-trig cyclization products were converted into 2-(methoxycarbonyl)-2-cyclopentene-1-carboxylic acid methyl ester in an excellent yield. 5-exo-trig cyclization of the unsymmetrical dienedioate consisting of crotonate and (E)-2-methyl-2-butenoate units proceeded regioselectively through conjugate addition of LSA to the crotonate part. Similar regioselectively was observed in the case of 5-exo-trig cyclization of the dienedioate possessing crotonate and (E)-3-methyl-2-pentenoate units. Total syntheses of the physiologically active cyclopentane monoterpenes (+/-)-dihydronepetalactone and (+/-)-isohydronepetalactone has been accomplished by this cyclization strategy. In addition, it has been demonstrated that LSA is a more efficient nitrogen nucleophile than LDA to cyclize omega-halo-alpha,beta-unsaturated esters.