6-oxo-4-(1,1,2,2-tetramethyl-1-silapropoxy)cyclohex-1-enecarbonitrile

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-oxo-4-(1,1,2,2-tetramethyl-1-silapropoxy)cyclohex-1-enecarbonitrile
• 英文别名: 4-[Tert-butyl(dimethyl)silyl]oxy-6-oxocyclohexene-1-carbonitrile
• 化学式: C₁₃H₂₁NO₂Si
• 分子量: 251.401
• InChiKey: GHBSLORTNRKNDU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.19
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  lithium dimethylcuprate 、 叔丁基二甲基氯硅烷 、 6-oxo-4-(1,1,2,2-tetramethyl-1-silapropoxy)cyclohex-1-enecarbonitrile 以 四氢呋喃 为溶剂， 反应 0.5h， 以27%的产率得到(+/-)-(4R,6R)-2,4-bis(1,1,2,2-tetramethyl-1-silapropoxy)-6-methylcyclohex-1-enecarbonitrile
  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 (5E)-3-oxooct-5-enoate 在 sodium tetrahydroborate 、 正丁基锂 、 臭氧 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 反应 6.17h， 生成 6-oxo-4-(1,1,2,2-tetramethyl-1-silapropoxy)cyclohex-1-enecarbonitrile
  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

文献信息

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

  DOI：10.15227/orgsyn.078.0254

  日期：——
• 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.