(S)-(-)-6-acetoxy-2-cyclohexenone | 737806-85-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-(-)-6-acetoxy-2-cyclohexenone
• 英文别名: (1S)-2-Oxocyclohex-3-en-1-yl acetate；[(1S)-2-oxocyclohex-3-en-1-yl] acetate
• CAS: 737806-85-8
• 化学式: C₈H₁₀O₃
• 分子量: 154.166
• InChiKey: FUSJDZULOVJEKS-QMMMGPOBSA-N

物化性质

• 沸点：
  242.5±40.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 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：

  (S)-(-)-6-acetoxy-2-cyclohexenone 在 四氧化锇 、 氧化-4-甲基吗啉一水合物 、 Florisil 、 水 、 sodium hydrogensulfite 作用下， 以 水 、 丙酮 为溶剂， 反应 38.0h， 以75%的产率得到(1S,3R,4R)-3,4-dihydroxy-2-oxocyclohexyl acetate
  参考文献：
  名称：

  通过化学酶法立体选择性合成旋光的环糖醇前体

  摘要：

  外消旋的α'-乙酰氧基α，β-不饱和环己酮已通过PLE的酶促拆分反应转化为相应的对映体富集的97％ee的α'-羟基化和乙酰氧基化的化合物。对映体富集的α'-乙酰氧基化化合物的OsO 4催化二羟基化以85％的化学收率提供了一个非对映异构体。通过X射线衍射分析确定2,3,6-三乙酰氧基环己酮的绝对构型。后续的Luche还原使我们能够得到对应的SYN按预期在高度立体选择性方式型环多醇的前体。

  DOI：

  10.1016/j.tetasy.2006.11.002
• 作为产物：
  描述：

  2-氧代-环己-3-烯基乙酸酯 在 ammonium sulfate 、 phosphate buffer 、 pig liver esterase 作用下， 反应 3.0h， 以46%的产率得到(S)-(-)-6-acetoxy-2-cyclohexenone
  参考文献：
  名称：

  Chemoenzymatic synthesis of α′- and α-acetoxylated cyclic ketones

  摘要：

  alpha,beta-Unsaturated and saturated cyclic ketones were selectively oxidized at the alpha'- and alpha-positions using Mn(OAc)(3) and Pb(OAc)(4), respectively, resulting in high chemical yields. The resultant racemic alpha'- and alpha-acetoxylated substrates were resolved into corresponding enantiomerically enriched alpha'- and alpha-hydroxylated and acetoxylated compounds with 96-98% ee via PLE hydrolysis. The absolute configurations of alpha'-acetoxy-alpha,beta-unsaturated cyclic ketones were determined by transforming them into the corresponding saturated alpha-acetoxy cyclic ketones of known absolute configuration. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.04.019

文献信息

• Total synthesis of (+)-blennolide C and (+)-gonytolide C via spirochromanone
  作者：Kanna Adachi、Sho Hasegawa、Kazuaki Katakawa、Takuya Kumamoto

  DOI：10.1016/j.tetlet.2017.10.038

  日期：2017.11

  We report the asymmetric total synthesis of (+)-blennolide C and (+)-gonytolide C isolated from endophytic fungi. The synthesis involved construction of a spirochromanone with a chiral quaternary carbon by the aldol reaction of o-hydroxyacetophenones and optically active α-oxygenated cyclohexenone, followed by cyclization under acidic conditions. Oxidative cleavage of the alkene moiety of the spirochromanone

  我们报告从内生真菌中分离出来的（+）-布兰诺利德C和（+）-gonytolide C的不对称总合成。一个spirochromanone的合成涉及的结构与通过醛醇缩合反应手性季碳ö -hydroxyacetophenones和光学活性的α-氧化环己烯酮，接着在酸性条件下环化。螺并苯并二氢吡喃酮的烯烃部分的氧化裂解提供了苯并二氢吡喃酮二酯。通过用路易斯酸处理二酯，通过去保护二酯的氧官能度并同时进行Dieckmann缩合反应，实现了（+）-亚油酸内酯C的第一个全合成。还可以通过由脱保护的二酯形成内酯来实现（+）-去甲内酯C的全合成。
• Chemoenzymatic synthesis of enantiomerically enriched 2-oxobicyclo[m.1.0]alkan-3-yl acetate derivatives
  作者：Fazilet Devrim Özdemirhan、Murat Çelik、Selin Atlı、Cihangir Tanyeli

  DOI：10.1016/j.tetasy.2006.01.004

  日期：2006.1

  α′-acetoxy α,β-unsaturated cyclopentanone and cyclohexanone have been resolved into the corresponding enantiomerically enriched α′-hydroxylated and acetoxylated compounds with 96–97% ee via PLE hydrolysis. Stereoselectivity in the palladium(II)-catalyzed reaction between the enantiomerically enriched α′-acetoxylated compounds and diazomethane has been investigated. In the α′-acetoxylated cyclopentenone

  外消旋的α'-乙酰氧基α，β-不饱和环戊酮和环己酮已通过PLE水解分解为相应的对映体富集的具有96-97％ee的α'-羟基化和乙酰氧基化的化合物。研究了对映体富集的α'-乙酰氧基化化合物与重氮甲烷之间在钯（II）催化反应中的立体选择性。在α'-乙酰氧基化的环戊烯酮中，优先的环丙烷化反应以反形式发生，而α'-乙酰氧基化的环己烯酮提供顺式和反式产物（syn：anti，61：36％）。通过NOE实验确定产物的相对构型。
• Chemoenzymatic synthesis of α′- and α-acetoxylated cyclic ketones
  作者：Cihangir Tanyeli、Engin Turkut、İdris Mecidoğlu Akhmedov

  DOI：10.1016/j.tetasy.2004.04.019

  日期：2004.6

  alpha,beta-Unsaturated and saturated cyclic ketones were selectively oxidized at the alpha'- and alpha-positions using Mn(OAc)(3) and Pb(OAc)(4), respectively, resulting in high chemical yields. The resultant racemic alpha'- and alpha-acetoxylated substrates were resolved into corresponding enantiomerically enriched alpha'- and alpha-hydroxylated and acetoxylated compounds with 96-98% ee via PLE hydrolysis. The absolute configurations of alpha'-acetoxy-alpha,beta-unsaturated cyclic ketones were determined by transforming them into the corresponding saturated alpha-acetoxy cyclic ketones of known absolute configuration. (C) 2004 Elsevier Ltd. All rights reserved.
• Stereoselective synthesis of optically active cyclitol precursors via a chemoenzymatic method
  作者：Funda Oğuzkaya、Ertan Şahin、Cihangir Tanyeli

  DOI：10.1016/j.tetasy.2006.11.002

  日期：2006.11

  Racemic α′-acetoxy α,β-unsaturated cyclohexanone has been converted to the corresponding enantiomerically enriched α′-hydroxylated and acetoxylated compounds with 97% ee via enzymatic resolution with PLE. OsO4-Catalyzed dihydroxylation of enantiomerically enriched α′-acetoxylated compound afforded a single diastereomer in 85% chemical yield. The absolute configuration of 2,3,6-triacetoxycylohexanone

  外消旋的α'-乙酰氧基α，β-不饱和环己酮已通过PLE的酶促拆分反应转化为相应的对映体富集的97％ee的α'-羟基化和乙酰氧基化的化合物。对映体富集的α'-乙酰氧基化化合物的OsO 4催化二羟基化以85％的化学收率提供了一个非对映异构体。通过X射线衍射分析确定2,3,6-三乙酰氧基环己酮的绝对构型。后续的Luche还原使我们能够得到对应的SYN按预期在高度立体选择性方式型环多醇的前体。