tert-butyl 2-acetyl-2-methyl-5-oxohexanoate | 918131-52-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: tert-butyl 2-acetyl-2-methyl-5-oxohexanoate
• 英文别名: tert-butyl (2S)-2-acetyl-2-methyl-5-oxohexanoate
• CAS: 918131-52-9
• 化学式: C₁₃H₂₂O₄
• 分子量: 242.315
• InChiKey: GDYXFCNNMQCUGG-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 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：

  2-甲基-3-氧代丁酸叔丁酯 、 丁烯酮 在 [Pd((S)-BINAP)(H2O)2](OTf)2 N-氟代双苯磺酰胺 作用下， 以 various solvent(s) 为溶剂， 反应 36.0h， 生成 tert-butyl 2-acetyl-2-methyl-5-oxohexanoate 、 tert-butyl 2-acetyl-2-methyl-5-oxohexanoate
  参考文献：
  名称：

  钯络合物在离子液体中的固定和再利用：有效的催化不对称氟化和与β-酮酸酯的迈克尔反应。

  摘要：

  [反应：见正文]将钯配合物（1和2）固定在离子液体中，并成功证明了其在催化不对称氟化和β-酮酸酯的迈克尔反应中的应用。这种固定化使得催化剂的再利用在氟化中的重复使用率不低于10次，在迈克尔反应中的重复使用率不低于5次，其效率水平可与常规有机溶剂中获得的水平相媲美。

  DOI：

  10.1021/ol035053a

文献信息

• Immobilization and Reuse of Pd Complexes in Ionic Liquid:  Efficient Catalytic Asymmetric Fluorination and Michael Reactions with β-Ketoesters
  作者：Yoshitaka Hamashima、Hisashi Takano、Daido Hotta、Mikiko Sodeoka

  DOI：10.1021/ol035053a

  日期：2003.9.1

  [reaction: see text] Palladium complexes (1 and 2) were immobilized in ionic liquids, and their applications to catalytic asymmetric fluorination and Michael reaction of beta-ketoesters were successfully demonstrated. This immobilization enabled the reuse of the catalysts no less than 10 times in fluorination and 5 times in Michael reaction with levels of efficiency comparable to those obtained in

  [反应：见正文]将钯配合物（1和2）固定在离子液体中，并成功证明了其在催化不对称氟化和β-酮酸酯的迈克尔反应中的应用。这种固定化使得催化剂的再利用在氟化中的重复使用率不低于10次，在迈克尔反应中的重复使用率不低于5次，其效率水平可与常规有机溶剂中获得的水平相媲美。
• 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 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。