2-methyl-1-tetralone-2-carboxylic acid benzyl ester | 188359-88-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-methyl-1-tetralone-2-carboxylic acid benzyl ester
• 英文别名: benzyl 2-methyl-1-tetralone-2-carboxylate；2-methyl-2-benzyloxycarbonyl-1-tetralone；Benzyl 2-methyl-1-oxo-3,4-dihydronaphthalene-2-carboxylate
• CAS: 188359-88-8
• 化学式: C₁₉H₁₈O₃
• 分子量: 294.35
• InChiKey: BXXKTCZGTZJCML-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 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-tetralone-2-carboxylic acid benzyl ester 在 palladium on activated charcoal 氢气 作用下， 以 乙腈 为溶剂， 反应 1.17h， 生成 2-methyl-1-tetralone-2-carboxylic acid
  参考文献：
  名称：

  Mechanistic Insights into the Palladium-Induced Domino Reaction Leading to Ketones from Benzyl β-Ketoesters:  First Characterization of the Enol as an Intermediate

  摘要：

  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.

  DOI：

  10.1021/jo049464w
• 作为产物：
  描述：

  二苄基碳酸盐[脂] 在 sodium hydroxide 、 sodium hydride 作用下， 以 甲苯 为溶剂， 反应 11.0h， 生成 2-methyl-1-tetralone-2-carboxylic acid benzyl ester
  参考文献：
  名称：

  Mechanistic Insights into the Palladium-Induced Domino Reaction Leading to Ketones from Benzyl β-Ketoesters:  First Characterization of the Enol as an Intermediate

  摘要：

  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.

  DOI：

  10.1021/jo049464w

文献信息

• 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。
• On the decarboxylation of 2-methyl-1-tetralone-2-carboxylic acid – oxidation of the enol intermediate by triplet oxygen
  作者：Abdelkhalek Riahi、Jacques Muzart、Manabu Abe、Norbert Hoffmann

  DOI：10.1039/c3nj00457k

  日期：——

  The formation of 2-methyl-1-tetralone from the metal-free and base-free decarboxylation of 2-methyl-1-tetralone-2-carboxylic acid involves 2-methyl-3,4-dihydro-1-naphthol as an intermediate. The reaction of this enol with atmospheric oxygen leads to 2-hydroperoxy-2-methyl-1-tetralone. The oxidation mechanism is confirmed by quantum chemical calculations at the (U)B3LYP/6-31G(d) level of theory.

  由2-甲基-1-四氢萘-2-羧酸的无金属和无碱脱羧反应生成2-甲基-1-四氢萘酮涉及 2-甲基-3,4-二氢-1-萘酚作为中间体。该烯醇与大气氧的反应产生2-氢过氧-2-甲基-1-四氢萘酮。氧化机理已通过理论（U）B3LYP / 6-31G（d）的量子化学计算得到证实。
• Enantioselective Decarboxylation of β-Keto Esters with Pd/Amino Alcohol Systems: Successive Metal Catalysis and Organocatalysis
  作者：Pavel Kukula、Václav Matoušek、Tamas Mallat、Alfons Baiker

  DOI：10.1002/chem.200701652

  日期：2008.3.17

  Pd-catalysed debenzylation of 1 to afford the corresponding beta-keto acid (2), there are two possible reaction routes that may be catalysed by the chiral amino alcohol in solution or by Pd(0) sites on the metal surface in cooperation with the adsorbed amino alcohol. The reaction intermediate 2 was synthesized, and the kinetics of decarboxylation were followed by NMR, UV and IR spectroscopy. The studies revealed

  研究了在Pd / C-手性氨基醇催化剂体系存在下，外消旋β-酮酸酯一锅级联反应生成手性酮的动力学和机理。在Pd / C存在下，将2-甲基-1-四氢萘-2-羧酸苄基酯（1）转化为2-甲基-1-四氢萘酮（4），并选择金鸡纳生物碱或麻黄碱作为模型反应。在第一步反应之后，钯催化的1的脱苄基反应得到相应的β-酮酸（2），有两种可能的反应路线可以由溶液中的手性氨基醇或Pd（0）上的位点催化与吸附的氨基醇协同作用的金属表面。合成反应中间体2，并通过NMR，UV和IR光谱跟踪脱羧的动力学。研究表明，Pd的作用是通过1的脱保护来触发反应系列。随后，从外消旋β-酮酸2到手性酮4的主要反应路线是在液相中由手性氨基醇催化的。结果表明，rac-2和手性氨基醇的非对映异构体盐的动力学拆分在对映体选择中起关键作用。高对映选择性要求氨基醇/ rac-2比率至少为2。高比率有利于形成1：1氨基醇/酸非对映异构体复合物，第二
• 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.