(1S,5S)-ethyl 1-ethyl-3-hydroxy-5-(4-methoxyphenyl)-4-methyl-2-oxocyclopent-3-enecarboxylate | 1228457-91-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (1S,5S)-ethyl 1-ethyl-3-hydroxy-5-(4-methoxyphenyl)-4-methyl-2-oxocyclopent-3-enecarboxylate
• 英文别名: ethyl (1S,5S)-1-ethyl-3-hydroxy-5-(4-methoxyphenyl)-4-methyl-2-oxocyclopent-3-enecarboxylate；ethyl (1S,2S)-1-ethyl-4-hydroxy-2-(4-methoxyphenyl)-3-methyl-5-oxocyclopent-3-ene-1-carboxylate
• CAS: 1228457-91-7
• 化学式: C₁₈H₂₂O₅
• 分子量: 318.37
• InChiKey: BQHORGWSCIEFEU-KDOFPFPSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (Z)-3-(4-甲氧基苯基)-2-甲基-丙-2-烯酸 在 tris-(dibenzylideneacetone)dipalladium(0) 、 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex 、 草酰氯 、 (1R,7R)-9,9-dimethyl-4-(N-phenyl-2-pyridylamino)-2,2,6,6-tetraphenyl-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decane 、 氟化氢吡啶 、 N,N-二甲基甲酰胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 64.0h， 生成 (1S,5S)-ethyl 1-ethyl-3-hydroxy-5-(4-methoxyphenyl)-4-methyl-2-oxocyclopent-3-enecarboxylate
  参考文献：
  名称：

  对映选择性钯（0）催化的Nazarov型环化

  摘要：

  描述了Pd 0催化的不对称Nazarov型环化反应。该反应的优化配体将弱配位吡啶环掺入TADDOL衍生的亚磷酰胺（TADDOL =α，α，α，α-四芳基-1,3-二氧戊环-4,5-二甲醇）。该反应导致形成单一非对映异构体的环戊烯酮，以高收率和光学纯度结合了两个连续的不对称中心，一个叔碳原子中心和一个全碳原子的四元立体中心。值得注意的是，该反应不需要底物应被芳基取代基活化。

  DOI：

  10.1002/anie.201500881

文献信息

• An Organocatalytic Asymmetric Nazarov Cyclization
  作者：Ashok K. Basak、Naoyuki Shimada、William F. Bow、David A. Vicic、Marcus A. Tius

  DOI：10.1021/ja103028r

  日期：2010.6.23

  An organocatalytic asymmetric Nazarov cyclization of diketoesters that proceeds by means of a dual activation mechanism has been developed. Screening of a number of catalysts led to a new thiourea that incorporates a primary amino group. The method gives rise to cyclic products with two adjacent quaternary asymmetric carbon atoms, one of which is an all-carbon stereocenter, with complete or nearly

  已经开发了通过双重活化机制进行的二酮酯的有机催化不对称 Nazarov 环化。对许多催化剂的筛选产生了一种新的硫脲，它包含一个伯氨基。该方法产生具有两个相邻季不对称碳原子的环状产物，其中一个是全碳立体中心，具有完全或几乎完全的非对映选择性和高或非常高的对映体过量。还描述了通过亲核加成到乙烯酮的无环二酮酯起始材料的简单且非常方便的合成。
• Neutral Nazarov-Type Cyclization Catalyzed by Palladium(0)
  作者：Naoyuki Shimada、Craig Stewart、William F. Bow、Anais Jolit、Kahoano Wong、Zhe Zhou、Marcus A. Tius

  DOI：10.1002/anie.201201724

  日期：2012.6.4

  Joining the circle: The first Pd0 catalyzed Nazarov‐type cyclization of diketoesters (see scheme) proceeds in 70 % to 95 % yield under strictly neutral pH conditions. Aryl substitution of the diketoesters is not required, so the reaction shows great versatility and can also proceed with aliphatic substrates.

  加入循环： 在严格中性 pH 条件下，第一个 Pd 0催化的 Nazarov 型二酮酯环化（见方案）以 70% 至 95% 的产率进行。不需要二酮酯的芳基取代，因此该反应显示出很大的通用性，也可以用脂肪族底物进行。
• Origins of the Stereoselectivity in a Thiourea–Primary Amine-Catalyzed Nazarov Cyclization
  作者：Austin H. Asari、Yu-hong Lam、Marcus A. Tius、K. N. Houk

  DOI：10.1021/jacs.5b08969

  日期：2015.10.14

  The origins of stereoselectivity of the Nazarov reactions of alpha-hydroxydivinylketones catalyzed by a vicinal thiourea primary amine first reported by Tius have been explored with density functional theory. The electrocyclization transition structures in which the thiourea group of the catalyst donates two hydrogen bonds to the keto carbonyl group of the Nazarov reactant and the primary amine accepts a hydrogen bond from the hydroxyl group of the reactant have been modeled. The enantiomeric Nazarov transition structures, which are conventionally described by the absolute sense of conrotation of the dienone termini ("clockwise" or "counter-clockwise") in the literature, are nonplanar and adopt helically chiral conformations. The interactions of these helical electrocyclization transition structures with the chiral catalyst are studied in detail. The organocatalyst is found to employ a combination of hydrogen bonding and steric effects to achieve helical recognition of the Nazarov transition state.