4-hydroxy-4-methyl-2-oxo-6-cyclohexenecarbonitrile | 190451-98-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-hydroxy-4-methyl-2-oxo-6-cyclohexenecarbonitrile
• 英文别名: 4-Hydroxy-4-methyl-6-oxocyclohexene-1-carbonitrile
• CAS: 190451-98-0
• 化学式: C₈H₉NO₂
• 分子量: 151.165
• InChiKey: MRXDPIUTOBSQLY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  61.1
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  甲基氯化镁 、 4-hydroxy-4-methyl-2-oxo-6-cyclohexenecarbonitrile 以 四氢呋喃 为溶剂， 反应 0.08h， 以51%的产率得到4-Hydroxy-2,4-dimethyl-6-oxo-cyclohexanecarbonitrile
  参考文献：
  名称：

  Unsaturated Oxo−Nitriles:  Stereoselective, Chelation-Controlled Conjugate Additions

  摘要：

  Addition of Grignard reagents to the unsaturated oxo-nitrile 10 (4-hydroxy-4-methyl-6-oxocyclohex-1-enecarbonitrile) provides conjugate addition products with virtually complete stereocontrol. Mechanistic evidence supports a chelation-controlled conjugate addition via alkylmagnesium alkoxide inter mediates. Diverse Grignard reagents having sp(3)-, sp(2)-, and sp-hybridized carbons react with comparable efficiency, with even sterically demanding nucleophiles adding with complete stereocontrol. Unsaturated oxo-nitriles that are incapable of chelation afford diastereomeric conjugate addition products through an unusual boatlike transition state. Collectively, these reactions illustrate the complementary stereoselectivity of chelation-controlled conjugate additions to hydroxylated, unsaturated oxo-nitriles and stereoelectronically controlled conjugate additions to enones.

  DOI：

  10.1021/jo9909709
• 作为产物：
  描述：

  ethyl 3-hydroxy-3-methyl-hex-5-enoate 在 正丁基锂 、 二甲基硫 、 臭氧 作用下， 反应 18.0h， 生成 4-hydroxy-4-methyl-2-oxo-6-cyclohexenecarbonitrile
  参考文献：
  名称：

  不饱和腈：多米诺骨牌臭氧分解-羟醛合成的前体。

  摘要：

  通过串联的臭氧分解-醛醇缩合序列制备环状的五元，六元和七元乙腈。环戊烯基乙腈（4）和环己烯基乙腈（12）通过高效的一锅合成法分别提供了扩环的乙腈3（98％）和17（58％）。通过使用ω-烯基β-酮腈的类似的臭氧分解-醛醇缩合环化来制备同源的五元氧腈22a-c。该方法耐受各种取代模式，并允许合成β，β-二取代的乙腈（22c）。反应条件基本上是中性的，仅向β-羟基氧腈22d和22e提供痕量的芳族脱水产物。

  DOI：

  10.1021/jo9822885

文献信息

• Unsaturated Nitriles:  A Domino Ozonolysis−Aldol Synthesis of Highly Reactive Oxonitriles
  作者：Fraser F. Fleming、Adrian Huang、Vaqar A. Sharief、Yifang Pu

  DOI：10.1021/jo9703818

  日期：1997.5.1
• 1-OXO-2-CYCLOHEXENYL-2-CARBONITRILE
  作者：Fleming, Fraser F.、Shook, Brian C.

  DOI：10.15227/orgsyn.078.0254

  日期：——
• Unsaturated Nitriles:  Precursors for a Domino Ozonolysis−Aldol Synthesis of Oxonitriles
  作者：Fraser F. Fleming、Adrian Huang、Vaqar A. Sharief、Yifang Pu

  DOI：10.1021/jo9822885

  日期：1999.4.1

  five-membered oxonitriles 22a-c are prepared by analogous ozonolysis-aldol cyclizations employing omega-alkenyl beta-ketonitriles. The method tolerates various substitution patterns and allows for the synthesis of beta,beta-disubstituted oxonitriles (22c). The reaction conditions are essentially neutral providing the beta-hydroxyoxonitriles 22d and 22e with only trace amounts of the aromatic dehydration

  通过串联的臭氧分解-醛醇缩合序列制备环状的五元，六元和七元乙腈。环戊烯基乙腈（4）和环己烯基乙腈（12）通过高效的一锅合成法分别提供了扩环的乙腈3（98％）和17（58％）。通过使用ω-烯基β-酮腈的类似的臭氧分解-醛醇缩合环化来制备同源的五元氧腈22a-c。该方法耐受各种取代模式，并允许合成β，β-二取代的乙腈（22c）。反应条件基本上是中性的，仅向β-羟基氧腈22d和22e提供痕量的芳族脱水产物。
• Unsaturated Oxo−Nitriles:  Stereoselective, Chelation-Controlled Conjugate Additions
  作者：Fraser F. Fleming、Jianping Guo、Qunzhao Wang、Douglas Weaver

  DOI：10.1021/jo9909709

  日期：1999.11.1

  Addition of Grignard reagents to the unsaturated oxo-nitrile 10 (4-hydroxy-4-methyl-6-oxocyclohex-1-enecarbonitrile) provides conjugate addition products with virtually complete stereocontrol. Mechanistic evidence supports a chelation-controlled conjugate addition via alkylmagnesium alkoxide inter mediates. Diverse Grignard reagents having sp(3)-, sp(2)-, and sp-hybridized carbons react with comparable efficiency, with even sterically demanding nucleophiles adding with complete stereocontrol. Unsaturated oxo-nitriles that are incapable of chelation afford diastereomeric conjugate addition products through an unusual boatlike transition state. Collectively, these reactions illustrate the complementary stereoselectivity of chelation-controlled conjugate additions to hydroxylated, unsaturated oxo-nitriles and stereoelectronically controlled conjugate additions to enones.