2-methyl-1-indanone-2-carboxylic acid benzyl ester | 188359-87-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: 2-methyl-1-indanone-2-carboxylic acid benzyl ester
• 英文别名: 2-methyl-2-benzyloxycarbonyl-1-indanone；benzyl 2-methyl-3-oxo-1H-indene-2-carboxylate
• CAS: 188359-87-7
• 化学式: C₁₈H₁₆O₃
• 分子量: 280.323
• InChiKey: JWJISQHIJBYZFL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-methyl-1-indanone-2-carboxylic acid benzyl ester 在 palladium on activated charcoal (+)-endo-2-hydroxy-endo-3-aminobornane 、 氢气 作用下， 以 乙腈 为溶剂， 反应 0.58h， 以86%的产率得到(R)-2-methyl-2,3-dihydro-1H-inden-1-one
  参考文献：
  名称：

  Asymmetric protonation of enolic species: dramatic increase in the selectivity with temperature and unexpected Eyring diagram

  摘要：

  The palladium-induced cleavage of beta-ketosters and enol carbonates derived from alpha-alkylated 1-indanones and 1-tetralones in the presence of (+)-endo-2-hydroxy-endo-3-aminobornane led to (R)-alpha-alkylated indanones and tetralones with a large increase in the enantioselectivity (up to 38-40%) when the reaction temperature was raised from 21 to 45-70 degrees C. Thus, enantiopure 2-methyl-1-indanone was obtained at 52 degrees C. More than one inversion temperature has appeared in plotting the corresponding Eyring diagrams. (C) 1997 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(97)84908-7
• 作为产物：
  描述：

  ethyl 2-methyl-1-indanone-2-carboxylate 、 苯甲醇 在 titanium(IV) isopropylate 作用下， 反应 3.0h， 生成 2-methyl-1-indanone-2-carboxylic acid benzyl ester
  参考文献：
  名称：

  Pd诱导的β-酮酯对映选择性脱保护-脱羧反应中的结构效应

  摘要：

  探索了三种不同的α，α-二取代苄基β-酮酸酯在Pd诱导的对映选择性脱羧（级联反应）中手性碱的结构效应和一些关键反应参数（催化剂类型和溶剂）的影响。合成了脱苄基反应后的反应中间体（β-酮基羧酸），并对其脱羧进行了独立研究。级联反应中的ee最高（高达60％）是通过那些含有芳环系统的底物和具有延伸的芳环（奎宁和奎尼丁）的手性氨基醇实现的。具有弱H键供体和受体性能的极性溶剂有利于对映体。

  DOI：

  10.1016/j.tetasy.2007.11.017

文献信息

• On the mechanism of the domino reaction of 2-methyl-2-benzyloxycarbonyl-1-indanone mediated by palladium, hydrogen and aminoalcohols
  作者：Caroline Muller、Françoise Hénin、Jacques Muzart

  DOI：10.3998/ark.5550190.p008.805

  日期：——

  Whereas the Pd-catalyzed hydrogenolysis of racemic 2-methyl-2-benzyloxycarbonyl-1-indanone in the presence of an unichiral (enantiopure) aminoalcohol leads to optically active 2methylindanone, such a domino reaction using optically active 2-methyl-2-benzyloxycarbonyl-1indanone and an achiral aminoalcohol affords racemic 2-methylindanone. According to these results, the ketone is obtained from the

  而在单手性（对映纯）氨基醇存在下，外消旋 2-甲基-2-苄氧基羰基-1-茚满酮的 Pd 催化氢解导致光学活性 2-甲基茚满酮，这种多米诺反应使用光学活性 2-甲基-2-苄氧基羰基- 1 茚满酮和非手性氨基醇生成外消旋 2-甲基茚满酮。根据这些结果，酮是从烯醇类物质的氨基醇介导的质子化中获得的。
• Mechanistic Insights into the Palladium-Induced Domino Reaction Leading to Ketones from Benzyl β-Ketoesters:  First Characterization of the Enol as an Intermediate
  作者：Jean-François Detalle、Abdelkhalek Riahi、Vincent Steinmetz、Françoise Hénin、Jacques Muzart

  DOI：10.1021/jo049464w

  日期：2004.10.1

  The monitoring by UV spectroscopy of the Pd-catalyzed hydrogenolysis in acetonitrile of 2-methyl-2-benzyloxycarbonyl-1-indanone and 2-methyl-2-benzyloxycarbonyl-1-tetralone showed the successive formation of corresponding beta-ketoacids and enols to deliver finally the ketones. Some factors which influence the stability of the intermediates are determined. In contrast to the above benzyl beta-ketoesters, the enol was not detected from benzyl (2-methylinden-3-yl) carbonate.
• β-Amino tertiary cycloalkanols for the enantioselective protonation of enolic species produced by a palladium-induced cascade reaction
  作者：S.Jamal Aboulhoda、I. Reiners、J. Wilken、F. Hénin、J. Martens、J. Muzart

  DOI：10.1016/s0957-4166(98)00189-x

  日期：1998.6

  The palladium-induced cleavage of beta-ketoesters and enol carbonates derived from alpha-alkylated 1-indanones and 1-tetralones in the presence of substoichiometric amounts of various (S)-aminocycloalkanols led to optically active (R)-alpha-alkylated indanones and tetralones with enantiomeric excesses of up to 72%. (C) 1998 Elsevier Science Ltd, All rights reserved.
• Structural effects in the Pd-induced enantioselective deprotection–decarboxylation of β-ketoesters
  作者：Pavel Kukula、Václav Matoušek、Tamas Mallat、Alfons Baiker

  DOI：10.1016/j.tetasy.2007.11.017

  日期：2007.12

  Structural effects in the chiral base and the influence of some key reaction parameters (catalyst type and solvent) in the Pd-induced enantioselective decarboxylation (cascade reaction) of three different α,α-disubstituted benzyl β-ketoesters were explored. The reaction intermediate after debenzylation (β-keto-carboxylic acid) was synthesized and its decarboxylation studied independently. The highest

  探索了三种不同的α，α-二取代苄基β-酮酸酯在Pd诱导的对映选择性脱羧（级联反应）中手性碱的结构效应和一些关键反应参数（催化剂类型和溶剂）的影响。合成了脱苄基反应后的反应中间体（β-酮基羧酸），并对其脱羧进行了独立研究。级联反应中的ee最高（高达60％）是通过那些含有芳环系统的底物和具有延伸的芳环（奎宁和奎尼丁）的手性氨基醇实现的。具有弱H键供体和受体性能的极性溶剂有利于对映体。
• Asymmetric protonation of enolic species: dramatic increase in the selectivity with temperature and unexpected Eyring diagram
  作者：Jacques Muzart、Françoise Hénin、Said Jamal Aboulhoda

  DOI：10.1016/s0957-4166(97)84908-7

  日期：1997.2

  The palladium-induced cleavage of beta-ketosters and enol carbonates derived from alpha-alkylated 1-indanones and 1-tetralones in the presence of (+)-endo-2-hydroxy-endo-3-aminobornane led to (R)-alpha-alkylated indanones and tetralones with a large increase in the enantioselectivity (up to 38-40%) when the reaction temperature was raised from 21 to 45-70 degrees C. Thus, enantiopure 2-methyl-1-indanone was obtained at 52 degrees C. More than one inversion temperature has appeared in plotting the corresponding Eyring diagrams. (C) 1997 Elsevier Science Ltd. All rights reserved.