ethyl (2S)-1-(cyclohexen-1-yl)pyrrolidine-2-carboxylate | 24738-82-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl (2S)-1-(cyclohexen-1-yl)pyrrolidine-2-carboxylate
• CAS: 24738-82-7
• 化学式: C₁₃H₂₁NO₂
• 分子量: 223.315
• InChiKey: ZYDPUDBRFSMCHF-LBPRGKRZSA-N

物化性质

• 沸点：
  323.3±41.0 °C(Predicted)
• 密度：
  1.087±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  乙酸烯丙酯 、 ethyl (2S)-1-(cyclohexen-1-yl)pyrrolidine-2-carboxylate 在 四(三苯基膦)钯 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 50.0h， 生成 (S)-2-allylcyclohexanone 、 (R)-2-allylcyclohexanone
  参考文献：
  名称：

  Asymmetric induction reactions. V. The palladium-catalyzed asymmetric .alpha.-allylation of carbonyl compounds with chiral allyl esters via enamines and imines

  摘要：

  A novel and excellent method for asymmetric alpha-allylation of carbonyl compounds via their chiral enamines or imines bearing allyl eaters has been developed. Readily available chiral allyl eaters having chirality at the alpha-position of the eater carbonyl group, such as (S)-proline and other (S)-alpha-amino acid allyl esters, have been found to serve as good asymmetric allylating reagents in palladium-catalyzed reactions of the chiral enamines and imines derived from them. The use of (S)-proline or (S)-valine allyl esters as the amino parts in the enamines or imines provided the highest optical yields of the corresponding alpha-allyl carbonyl compounds. A mechanism for asymmetric induction is proposed based on the stereochemical results obtained.

  DOI：

  10.1021/jo00080a033
• 作为产物：
  描述：

  环己酮 、 (2S)-吡咯烷-2-羧酸乙酯 以 苯 为溶剂， 反应 4.0h， 生成 ethyl (2S)-1-(cyclohexen-1-yl)pyrrolidine-2-carboxylate
  参考文献：
  名称：

  Asymmetric induction reactions. V. The palladium-catalyzed asymmetric .alpha.-allylation of carbonyl compounds with chiral allyl esters via enamines and imines

  摘要：

  A novel and excellent method for asymmetric alpha-allylation of carbonyl compounds via their chiral enamines or imines bearing allyl eaters has been developed. Readily available chiral allyl eaters having chirality at the alpha-position of the eater carbonyl group, such as (S)-proline and other (S)-alpha-amino acid allyl esters, have been found to serve as good asymmetric allylating reagents in palladium-catalyzed reactions of the chiral enamines and imines derived from them. The use of (S)-proline or (S)-valine allyl esters as the amino parts in the enamines or imines provided the highest optical yields of the corresponding alpha-allyl carbonyl compounds. A mechanism for asymmetric induction is proposed based on the stereochemical results obtained.

  DOI：

  10.1021/jo00080a033

文献信息

• Palladium-catalysed asymmetric allylations by a chiral allyl ester; the palladium catalysis of (S)-proline allyl ester enamines
  作者：Kunio Hiroi、Kyoko Suya、Shuko Sato

  DOI：10.1039/c39860000469

  日期：——

  The palladium-catalysed allylation of the chiral enamines (1a–d) followed by acidic hydrolysis, produced optically active 2-allylcyclohexanone (2); the catalysis of the chiral enamine (1a), derived from (S)-proline allyl ester, with tetrakis(triphenyl phosphine)palladium and subsequent acidic hydrolysis led to an almost 100% optical yield of (S)-(–)-(2).

  钯催化手性烯胺的烯丙基化（1a - d），然后进行酸水解，生成光学活性的2-烯丙基环己酮（2）；（S）-脯氨酸烯丙基酯衍生的手性烯胺（1a）与四（三苯基膦）钯催化并随后进行酸水解导致（S）-（-）-（2）的光学收率几乎达到100％）。