tert-butyl 2-oxo-1-(3-oxopentyl)cyclopentanecarboxylate

• 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: tert-butyl 2-oxo-1-(3-oxopentyl)cyclopentanecarboxylate
• 英文别名: tert-butyl (1R)-2-oxo-1-(3-oxopentyl)cyclopentane-1-carboxylate
• 化学式: C₁₅H₂₄O₄
• 分子量: 268.353
• InChiKey: YKEVQDCTPJJYTA-OAHLLOKOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1-戊烯-3-酮 、 tert-butyl 2-oxocyclopentanecarboxylate 在 {Pd(H₂O)2[(R_a)-BINAP]}⁽²⁺⁾*2TfO^(1-) 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 生成 tert-butyl 2-oxo-1-(3-oxopentyl)cyclopentanecarboxylate 、 tert-butyl 2-oxo-1-(3-oxopentyl)cyclopentanecarboxylate
  参考文献：
  名称：

  1,3-二羰基化合物的催化不对称Michael加成反应通过手性烯醇钯形成

  摘要：

  使用手性钯配合物已经开发了有效的催化对映选择性迈克尔反应。包括β-酮酸酯和1,3-二酮在内的各种底物与α，β-不饱和羰基化合物反应，以高达99％ee的高收率得到相应的迈克尔加合物，从而提供了手性季碳中心。在这些反应中，生成了手性钯烯醇盐作为关键中间体，它们与强质子酸协同作用，激活了迈克尔受体，从而促进了CC键形成反应。

  DOI：

  10.1002/adsc.200505199

文献信息

• Catalytic Enantioselective Michael Reaction of 1,3-Dicarbonyl Compoundsvia Formation of Chiral Palladium Enolate
  作者：Yoshitaka Hamashima、Daido Hotta、Natsuko Umebayashi、Yasunori Tsuchiya、Takeyuki Suzuki、Mikiko Sodeoka

  DOI：10.1002/adsc.200505199

  日期：2005.10

  catalytic enantioselective Michael reaction has been developed using chiral palladium complexes. Various substrates including β-keto esters and 1,3-diketones reacted with α,β-unsaturated carbonyl compounds to give the corresponding Michael adducts in good yield with up to 99% ee, thereby affording chiral quaternary carbon centers. In these reactions, chiral palladium enolates were generated as key intermediates

  使用手性钯配合物已经开发了有效的催化对映选择性迈克尔反应。包括β-酮酸酯和1,3-二酮在内的各种底物与α，β-不饱和羰基化合物反应，以高达99％ee的高收率得到相应的迈克尔加合物，从而提供了手性季碳中心。在这些反应中，生成了手性钯烯醇盐作为关键中间体，它们与强质子酸协同作用，激活了迈克尔受体，从而促进了CC键形成反应。
• Chiral lewis acid‐catalyzed enantioselective michael reactions in water
  作者：Shū Kobayashi、Kentaro Kakumoto、Yuichiro Mori、Kei Manabe

  DOI：10.1560/6grq-yrvv-6ku3-rhgx

  日期：2001.12

  Asymmetric Michael reactions of ß-ketoesters with enones were effectively catalyzed by complexes of silver salts and BINAP derivatives in water. The reactions have proved to give Michael adducts in high yields with high enantioselectivities. These reactions are the first example of Lewis acid-catalyzed asymmetric Michael reactions in water.

  银盐和BINAP衍生物在水中的络合物可有效催化ß-酮酸酯与烯酮的不对称Michael反应。已证明该反应以高收率和高对映选择性产生迈克尔加合物。这些反应是路易斯酸催化的水中不对称迈克尔反应的第一个例子。
• Direct Generation of Nucleophilic Chiral Palladium Enolate from 1,3-Dicarbonyl Compounds:  Catalytic Enantioselective Michael Reaction with Enones
  作者：Yoshitaka Hamashima、Daido Hotta、Mikiko Sodeoka

  DOI：10.1021/ja027075i

  日期：2002.9.1

  Generation of chiral palladium enolates from 1,3-dicarbonyl compounds with the palladium aqua complex and its application to the highly efficient catalytic enantioselective Michael reaction with enones are described. The palladium aqua complexes are likely to supply Brønsted base and Brønsted acid successively during the reaction. The former activates the carbonyl compounds to give chiral palladium enolates, and the latter cooperatively activates enones. Using a catalytic amount (2-10 mol %) of the palladium complexes, the various 1,3-dicarbonyl compounds including diketones and beta-ketoesters were converted to the desired Michael adducts in good yields (69-92%) with excellent enantiomeric excesses (89-99% ee).
• Catalytic Enantioselective Addition of Cyclic β-Keto Esters with Activated Olefins and N-Boc Imines Using Chiral <i>C</i>₂-Symmetric Cationic Pd²⁺ N-Heterocyclic Carbene (NHC) Diaqua Complexes
  作者：Zhen Liu、Min Shi

  DOI：10.1021/om100331z

  日期：2010.6.28

  The asymmetric addition of cyclic β-keto esters to activated olefins and N-Boc imines was realized by using chiral cationic C2-symmetric N-heterocyclic carbene (NHC) Pd2+ diaqua complexes 1a,b as the catalysts, producing the corresponding adducts in moderate to high yields (up to 95%) and with good to high enantioselectivities (up to 96% ee). Nevertheless, the most significant observation is that when

  通过使用手性阳离子C 2对称的N-杂环卡宾（NHC）Pd 2+ diaqua配合物1a，b作为催化剂，将环状β-酮酯不对称加成到活化烯烃和N-Boc亚胺上，生成相应的加合物具有中等至高收率（高达95％）和良好至高对映选择性（高达96％ee）。然而，最重要的观察结果是，当在这些反应中使用（R）-NHC Pd 2+ diadia配合物时，与从（R）-膦配体获得的催化剂相比，观察到了不同的绝对构型。