trans-(E,E)-4,11-diacetyl-5,12-dioxo-6,13-dioxa-1,8-cyclotetradecadiene

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: trans-(E,E)-4,11-diacetyl-5,12-dioxo-6,13-dioxa-1,8-cyclotetradecadiene
• 英文别名: 4,11-diacetyl-5,12-dioxo-6,13-dioxa-1,8-cyclotetradecadiene；(3R,5E,10S,12E)-3,10-diacetyl-1,8-dioxacyclotetradeca-5,12-diene-2,9-dione
• 化学式: C₁₆H₂₀O₆
• 分子量: 308.331
• InChiKey: GLIUHFGPANSHFK-NGWMXHLJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  86.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  乙酰乙酸烯丙酯 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 trans-(E,E)-4,11-diacetyl-5,12-dioxo-6,13-dioxa-1,8-cyclotetradecadiene
  参考文献：
  名称：

  Studies on the α-acetylation of δ-valerolactone and ε-caprolactone

  摘要：

  The synthetic approach to alpha-acetylated delta-valero- (7a) and epsilon-caprolactone (7b) is reported. While 7a was isolated in 21% yield from the respective iodoester 5a by an alkylation sequence involving transesterification and Finkelstein reaction, 7b was not obtained from 5b but the dimer 8. Also transesterification and olefin ring closing metathesis (RCM) failed to prepare 7b. RCM resulted in the dimeric lactone 10, showing that the formation of 14-membered rings is favored over that of seven-membered rings. A Mukaiyama-type Claisen reaction finally gave alpha-acetyl lactones 7a and 7b in practically useful quantity of about 10 g (62% yield): starting lactones 13a,b were converted to silylenolethers 14a,b, which were acetylated with acetic anhydride in presence of the Lewis acid catalyst TiCl4. However, acetylation depends on the addition sequence of starting materials: if the mixture of Ac2O/TiCl4 is added to 14b, lactone 7b can be further converted to give bis-oxepanonyl ethanols 15a,b. Both compounds 15 were characterized by X-ray crystallography and NMR. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00511-8

文献信息

• Synthesis of α-Acetyl Lactones; Access to 14-Membered Bislactones by Attempts at Direct Ring Closure
  作者：Jens Christoffers、Heiko Oertling、Peter Fischer、Wolfgang Frey

  DOI：10.1055/s-2002-31907

  日期：——

  α-Acetyl lactones are accessed by Mukaiyama-Claisen reactions. Attempts at direct 7-membered ring closure, by either intramolecular alkylation of 4-iodobutyl acetoacetate or olefin metathesis from allyl 2-allyl-3-oxobutanoate, afford exclusively dimeric 14-membered ring products instead of the expected caprolactones.

  α-乙酰内酯可通过向山-克莱森反应获得。通过 4-碘丁基乙酰乙酸酯的分子内烷基化或 2-烯丙基-3-氧代丁酸烯丙酯的烯烃复分解，尝试直接 7 元环闭合，仅提供二聚体 14 元环产物而不是预期的己内酯。
• Studies on the α-acetylation of δ-valerolactone and ε-caprolactone
  作者：Jens Christoffers、Heiko Oertling、Peter Fischer、Wolfgang Frey

  DOI：10.1016/s0040-4020(03)00511-8

  日期：2003.5

  The synthetic approach to alpha-acetylated delta-valero- (7a) and epsilon-caprolactone (7b) is reported. While 7a was isolated in 21% yield from the respective iodoester 5a by an alkylation sequence involving transesterification and Finkelstein reaction, 7b was not obtained from 5b but the dimer 8. Also transesterification and olefin ring closing metathesis (RCM) failed to prepare 7b. RCM resulted in the dimeric lactone 10, showing that the formation of 14-membered rings is favored over that of seven-membered rings. A Mukaiyama-type Claisen reaction finally gave alpha-acetyl lactones 7a and 7b in practically useful quantity of about 10 g (62% yield): starting lactones 13a,b were converted to silylenolethers 14a,b, which were acetylated with acetic anhydride in presence of the Lewis acid catalyst TiCl4. However, acetylation depends on the addition sequence of starting materials: if the mixture of Ac2O/TiCl4 is added to 14b, lactone 7b can be further converted to give bis-oxepanonyl ethanols 15a,b. Both compounds 15 were characterized by X-ray crystallography and NMR. (C) 2003 Elsevier Science Ltd. All rights reserved.

表征谱图