5-氧代-3-环己烯-1-羧酸甲酯 | 37051-55-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 5-氧代-3-环己烯-1-羧酸甲酯
• 英文名称: 1-methoxycarbonyl-4-cyclohexen-3-one
• 英文别名: methyl 5-oxo-3-cyclohexene-1-carboxylate；methyl-1-cyclohexene-1-carboxylate；5-oxo-cyclohex-3-enecarboxylic acid methyl ester；5-Oxo-cyclohex-3-encarbonsaeure-methylester；Methyl 5-oxocyclohex-3-ene-1-carboxylate
• CAS: 37051-55-1
• 化学式: C₈H₁₀O₃
• 分子量: 154.166
• InChiKey: AKPIJBFSCOEJSB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  5-氧代-3-环己烯-1-羧酸甲酯 在 4-二甲氨基吡啶 、 lithium diisopropyl amide 作用下， 以 二氯甲烷 为溶剂， 反应 5.08h， 生成 5,12-Bis-(2,2-dimethyl-propionyloxy)-6,7,11-trimethoxy-4-oxo-1,2,3,4-tetrahydro-naphthacene-2-carboxylic acid methyl ester
  参考文献：
  名称：

  Synthesis and Chemistry of Quinone Methide Models for the Anthracycline Antitumor Antibiotics

  摘要：

  In an effort to further understand the chemistry of anthracycline-type quinone methides, two tetracyclic o-quinone methides, 4,5,12-trimethoxy-11-[(trimethylacetyl)oxy]-3-9,10-dihydro-6(2H)-naphthacenone (19) and (+/-)-9-carbomethoxy-4,5,12-trimethoxy-11-[(trimethylacetyl)oxy]-9,10-di-hydro-6(2H)-naphthacenone (20), were synthesized, and their reaction with several nucleophiles was investigated. Carbon-and sulfur-based nucleophiles afforded stable adducts while oxygen-and nitrogen-based nucleophiles afforded unstable adducts due to the reversibility of the addition. Adducts of 19 with ethanol and O-silylated adenosine (27) were acetylated to afford stable phenol acetates 21 and 29, respectively.

  DOI：

  10.1021/jo970539o
• 作为产物：
  描述：

  3-Oxo-4-p-tolylsulfanyl-cyclohexanecarboxylic acid methyl ester 在 sodium periodate 作用下， 以 四氯化碳 为溶剂， 生成 5-氧代-3-环己烯-1-羧酸甲酯
  参考文献：
  名称：

  3-(对甲苯硫基)-2-(三甲基甲硅烷氧基)-1,3-丁二烯的简单合成和Diels-Alder反应

  摘要：

  在二异丙基乙胺的存在下，3-(对甲苯基亚磺酰基)-2-丁酮与三氟甲磺酸三甲基甲硅烷基酯的反应定量地得到3-(对甲苯基硫基)-2-(三甲基甲硅烷氧基)-1,3-丁二烯(2)。研究了 2 和相关二烯与丙烯酸甲酯的 Diels-Alder 反应。

  DOI：

  10.1246/cl.1991.1577

文献信息

• Metal-Free I₂ -Catalyzed Highly Selective Dehydrogenative Coupling of Alcohols and Cyclohexenones
  作者：Yu-Feng Liang、Yizhi Yuan、Tao Shen、Song Song、Ning Jiao

  DOI：10.1002/cjoc.201700743

  日期：2018.3

  synthesis of aryl alkyl ethers has been described. DMSO is employed as the mild terminal oxidant. This novel methodology offers a metal‐free reaction condition, operational simplicity and broad substrate scope to afford valuable products from inexpensive reagents. Various meta‐substituted aromatic ethers which are hardly synthesized from the reported methods requiring meta‐substituted phenols, are efficiently

  已经描述了I 2催化的环己酮和醇的高度选择性氧化缩合，用于合成芳基烷基醚。DMSO被用作温和的终端氧化剂。这种新颖的方法提供了无金属的反应条件，操作简便性和广泛的底物范围，可从廉价的试剂中获得有价值的产品。通过本方案可以有效地制备各种难以从报道的需要间位取代的苯酚的方法合成的间位取代的芳族醚。
• Palladium-Catalyzed Chemo- and Enantioselective Oxidation of Allylic Esters and Carbonates
  作者：Barry M. Trost、Jeffery Richardson、Kelvin Yong

  DOI：10.1021/ja057163d

  日期：2006.3.1

  oxidation of allylic esters and carbonates using a novel potassium nitronate has been developed. This method is highly chemoselective, leaving other esters, alcohols, thioethers, and amines undisturbed. The oxidation can be operated in two modes: an achiral mode, using either PPh3 or rac-2 as ligand, or a chiral and highly enantioselective mode, using 2 as ligand. The oxidative enantioselective desymmetrization

  已经开发了使用新型硝酸钾的钯催化氧化烯丙酯和碳酸酯。该方法具有高度化学选择性，不会干扰其他酯、醇、硫醚和胺。氧化可以以两种模式进行：非手性模式，使用 PPh3 或 rac-2 作为配体，或手性和高度对映选择性模式，使用 2 作为配体。与其他策略相比，内消旋双酯的氧化对映选择性去对称化提供了一种明显更短的方法来获得常用的合成中间体。使用这种方法也可以实现高效的动力学拆分。
• The conjugate addition of a silyl group to enones and its removal with copper(<scp>II</scp>) bromide: a protecting group for the αβ-unsaturation of αβ-unsaturated ketones
  作者：David J. Ager、Ian Fleming、Shailesh K. Patel

  DOI：10.1039/p19810002520

  日期：——

  copper(I) salts react with enones, including esters and aldehydes, to give β-silyl carbonyl compounds in good yield. The β-silylketones can be used in synthesis without risk to the silyl group and the enone group can be restored by bromination-desilylbromination with copper(II) bromide. The principle is illustrated with syntheses of carvone and dihydrojasmone.

  与铜（I）盐混合的甲硅烷基锂试剂与烯酮（包括酯和醛）反应，以高收率得到β-甲硅烷基羰基化合物。β-甲硅烷基酮可用于合成而没有甲硅烷基基团的风险，并且烯酮基团可通过用溴化铜（II）进行溴化-脱甲硅烷基溴化来恢复。香芹酮和二氢茉莉酮的合成说明了该原理。
• Novel oxidative transformation: regiospecific preparation of naturally occurring 1-hydroxyanthraquinones
  作者：Frank M. Hauser、Subbarao Prasanna

  DOI：10.1021/jo00341a050

  日期：1982.1
• Murty; Hazra; Datta, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1997, vol. 36, # 2, p. 126 - 132
  作者：Murty、Hazra、Datta、Mal

  DOI：——

  日期：——