4-methoxy-3-methyl-2-oxocyclopent-3-en-1-yl acetate | 62966-13-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methoxy-3-methyl-2-oxocyclopent-3-en-1-yl acetate
• 英文别名: 5-Acetoxy-3-methoxy-2-methyl-2-cyclopentenon；(4-Methoxy-3-methyl-2-oxocyclopent-3-en-1-yl) acetate
• CAS: 62966-13-6
• 化学式: C₉H₁₂O₄
• 分子量: 184.192
• InChiKey: YRALMTCHLAIQHO-UHFFFAOYSA-N

物化性质

• 沸点：
  291.2±40.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-methoxy-3-methyl-2-oxocyclopent-3-en-1-yl acetate 在 lithium aluminium tetrahydride 、 pig liver esterase 、 potassium phosphate buffer 作用下， 以 乙醚 、 二甲基亚砜 为溶剂， 反应 16.0h， 生成 (R)-4-hydroxy-2-methylcyclopent-2-en-1-one
  参考文献：
  名称：

  A new and efficient chemoenzymatic route to both enantiomers of α′-acetoxy-α-methyl and γ-hydroxy-α-methyl cyclic enones

  摘要：

  A chemoenzymatic synthesis of both enantiomers of the pharmacologically interesting alpha'-acetoxy-alpha-methyl and gamma-hydroxy-alpha-methyl cyclic enones starting from alpha-methyl-beta-methoxy cyclic enones is reported. Manganese(Ill) acetate-mediated acetoxylation followed by the enzyme-mediated hydrolysis of alpha'-acetoxy enone provides acetoxy enones 1a and 2a and hydroxy enones 1b and 2b with high enantiomeric excesses in good yields. The reduction of the acetoxy and hydroxy enones furnished both enantiomers of gamma-hydroxy-alpha-methyl cyclic enones 3 and 4 in a high enantiomeric excess. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.12.006
• 作为产物：
  描述：

  3-methoxy-2-methylcyclopent-2-enone 、 manganese triacetate 以 苯 为溶剂， 生成 4-methoxy-3-methyl-2-oxocyclopent-3-en-1-yl acetate
  参考文献：
  名称：

  A new and efficient chemoenzymatic route to both enantiomers of α′-acetoxy-α-methyl and γ-hydroxy-α-methyl cyclic enones

  摘要：

  A chemoenzymatic synthesis of both enantiomers of the pharmacologically interesting alpha'-acetoxy-alpha-methyl and gamma-hydroxy-alpha-methyl cyclic enones starting from alpha-methyl-beta-methoxy cyclic enones is reported. Manganese(Ill) acetate-mediated acetoxylation followed by the enzyme-mediated hydrolysis of alpha'-acetoxy enone provides acetoxy enones 1a and 2a and hydroxy enones 1b and 2b with high enantiomeric excesses in good yields. The reduction of the acetoxy and hydroxy enones furnished both enantiomers of gamma-hydroxy-alpha-methyl cyclic enones 3 and 4 in a high enantiomeric excess. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.12.006

文献信息

• Potassium permanganate/carboxylic acid/organic solvent: a powerful reagent for enone oxidation and aryl coupling reactions
  作者：Ayhan S. Demir、Hamide Findik

  DOI：10.1016/j.tet.2008.05.004

  日期：2008.6

  with potassium permanganate and acetic acid, in which acetoxylation products were obtained in 74–96% yields. The same reaction was carried out with carboxylic acids other than acetic acid, which furnished corresponding acyloxy ketones with the same regioselectivity. For the first time, formyloxylation products were synthesized in a 61–85% yield by using formic acid. The potassium permanganate and acetic

  用高锰酸钾和乙酸进行烯酮的α'-乙酰氧基化和芳族酮的α-乙酰氧基化，得到乙酰氧基化产物的产率为74-96％。用乙酸以外的羧酸进行相同的反应，这提供了具有相同区域选择性的相应的酰氧基酮。首次使用甲酸以61-85％的产率合成了甲酰氧基化产物。高锰酸钾和乙酸法也用于芳基偶联反应。苯中的芳基硼酸和芳基肼与高锰酸钾和乙酸的反应反过来提供了85-96％的收率。我们已经证明高锰酸钾/羧酸/有机溶剂的行为像乙酸锰（III）。
• Stereochemical studies. 46. Studies on the synthesis of 4-acetoxy-cyclopentane-1,3-dione derivatives.
  作者：MUTSUYOSHI KITAMOTO、SHIRO TERASHIMA、SHUNICHI YAMADA

  DOI：10.1248/cpb.25.41

  日期：——

  As methods for preparing 4-acetoxy-cyclopentane-1, 3-dione derivatives (1), two synthetic schemes were examined. While the successive catalytic reduction and acetylation of cyclopentane-1, 3, 4-triones (2) according to the reported procedure gave the desired 1, the acid-catalyzed condensation of O-acetyl malic anhydride (3) with isopropenyl acetate (4a) and diethyl ketone enol acetate (4b) gave 2-carboxymethyl-5-methyl-3-oxo-2, 3-dihydrofuran (6a) and its 4-methyl derivative (6b), respectively, as the sole isolable product. The structures of 6a and 6b were elucidated from their chemical and spectroscopic behavior. Plausible formation mechanism for the compounds was also proposed.

  作为制备 4-乙酰氧基环戊烷-1, 3-二酮衍生物（1）的方法，我们研究了两种合成方案。根据已报道的程序，环戊烷-1，3，4-三酮（2）通过连续催化还原和乙酰化得到了所需的 1、在酸催化下，O-乙酰基苹果酸酐（3）与乙酸异丙烯酯（4a）和乙酸二乙酮烯醇酯（4b）缩合，分别得到 2-羧甲基-5-甲基-3-氧代-2，3-二氢呋喃（6a）及其 4-甲基衍生物（6b），作为唯一可分离的产物。6a 和 6b 的结构是从它们的化学和光谱行为中阐明的。还提出了这些化合物的合理形成机制。
• The Oxidation of β-Alkoxycyclopentenones and β-Alkoxycyclohexenones to α′-Acyloxy Derivatives Using Manganese(III) Acetate in Combination with Carboxylic Acids
  作者：Ayhan S. Demir、Tugmac Sayrac、David S. Watt

  DOI：10.1055/s-1990-27108

  日期：——

  The α′-oxidation of cyclic derivatives of β-alkoxy-α,β-unsaturated ketones using manganese(III) acetate in the presence of various carboxylic acids provided a convenient synthesis of 5-acyloxy-3-alkoxy-2-cyclopentenones and 6-acyloxy-3-alkoxy-2-cyclohexenones.

  在各种羧酸存在下，使用乙酸锰（III）对δ-烷氧基-δ,δ-不饱和酮的环状衍生物进行δ′-氧化，可方便地合成 5-乙酰氧基-3-烷氧基-2-环戊烯酮和 6-乙酰氧基-3-烷氧基-2-环己烯酮。
• DEMIR, AYHAN S.;SAYRAC, TUGMAC;WATT, DAVID S., SYNTHESIS (BRD),(1990) N2, C. 1119-1121
  作者：DEMIR, AYHAN S.、SAYRAC, TUGMAC、WATT, DAVID S.

  DOI：——

  日期：——