(+/-)-6-acetoxy-3-methoxycyclohex-2-en-1-one | 366024-06-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-6-acetoxy-3-methoxycyclohex-2-en-1-one
• 英文别名: 6-acetoxy-3-methoxy-2-cyclohexen-1-one；4-Methoxy-2-oxocyclohex-3-en-1-yl acetate；(4-methoxy-2-oxocyclohex-3-en-1-yl) acetate
• CAS: 366024-06-8
• 化学式: C₉H₁₂O₄
• 分子量: 184.192
• InChiKey: VGEPTHLWVBRAHT-UHFFFAOYSA-N

物化性质

• 沸点：
  298.8±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：

  (+/-)-6-acetoxy-3-methoxycyclohex-2-en-1-one 在 scandium tris(trifluoromethanesulfonate) 作用下， 以 甲醇 、 phosphate buffer 、 二甲基亚砜 为溶剂， 生成 (R)-6-Hydroxy-3-methoxy-cyclohex-2-enone
  参考文献：
  名称：

  A New and Efficient Chemoenzymatic Route to Both Enantiomers of 4-Hydroxycyclohex-2-en-1-one

  摘要：

  [GRAPHIC]A chemoenzymatic synthesis of both enantiomers of the pharmacologically interesting 4-hydroxycyclohex-2-en-1-one in three steps starting from 3-methoxycyclohex-2-en-1-one is described. Manganese(Ill) acetate-mediated acetoxylation followed by enzyme-mediated hydrolysis of a-acetoxy enone affords acetoxy enone 3 and hydroxy enone 4 with high enantiomeric excesses and in good yields. The reduction of the acetoxy and hydroxy enones furnished both enantiomers of 4-hydroxycyclohex-2-en-1-one in high enantiomeric excess.

  DOI：

  10.1021/ol025847+
• 作为产物：
  描述：

  (R)-6-acetoxy-3-methoxycyclohex-2-en-1-one 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 (+/-)-6-acetoxy-3-methoxycyclohex-2-en-1-one
  参考文献：
  名称：

  A New and Efficient Chemoenzymatic Route to Both Enantiomers of 4-Hydroxycyclohex-2-en-1-one

  摘要：

  [GRAPHIC]A chemoenzymatic synthesis of both enantiomers of the pharmacologically interesting 4-hydroxycyclohex-2-en-1-one in three steps starting from 3-methoxycyclohex-2-en-1-one is described. Manganese(Ill) acetate-mediated acetoxylation followed by enzyme-mediated hydrolysis of a-acetoxy enone affords acetoxy enone 3 and hydroxy enone 4 with high enantiomeric excesses and in good yields. The reduction of the acetoxy and hydroxy enones furnished both enantiomers of 4-hydroxycyclohex-2-en-1-one in high enantiomeric excess.

  DOI：

  10.1021/ol025847+

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）。
• Synthesis of antifungal alatanone and trineurone polyketides
  作者：Alexander R. Lewis、Keith P. Reber

  DOI：10.1016/j.tetlet.2016.01.090

  日期：2016.3

  The antifungal polyketides alatanones A and B and trineurones A–E have been synthesized using a one-pot C-acylation reaction coupling 1,3-cyclohexanediones with the appropriate carboxylic acids. This key transformation is believed to proceed via initial carbodiimide-mediated O-acylation followed by a DMAP-catalyzed Claisen–Haase rearrangement, resulting in O to C acyl migration.

  抗霉菌的聚酮化合物A和B以及三氮酮A-E是通过一锅C-酰化反应合成的，将1，3-环己二酮与适当的羧酸偶联。据信，这种关键的转化是通过最初的碳二亚胺介导的O-酰化，然后是DMAP催化的Claisen-Haase重排进行的，从而导致O到C的酰基迁移。