4a-hydroxymethyl-4,4a,5,6,7,8-hexahydro-(3H)-naphthalene-2-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4a-hydroxymethyl-4,4a,5,6,7,8-hexahydro-(3H)-naphthalene-2-one
• 英文别名: (4aR)-4a-(hydroxymethyl)-3,4,5,6,7,8-hexahydronaphthalen-2-one
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: KBQVEDVCPDYJBM-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-oxo-1-(3-oxo-butyl)-cyclohexanecarboxylic acid ethyl ester 在 四氢吡咯 、 盐酸 、 lithium aluminium tetrahydride 、 TMSSOTf 、 溶剂黄146 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 98.0h， 生成 4a-hydroxymethyl-4,4a,5,6,7,8-hexahydro-(3H)-naphthalene-2-one
  参考文献：
  名称：

  Direct Generation of Nucleophilic Chiral Palladium Enolate from 1,3-Dicarbonyl Compounds:  Catalytic Enantioselective Michael Reaction with Enones

  摘要：

  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).

  DOI：

  10.1021/ja027075i

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。
• 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).