4,4-dimethyl-3-<(Z)-3-(N-morpholino)-1-propenyl>cyclohexanone | 144758-40-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: 4,4-dimethyl-3-<(Z)-3-(N-morpholino)-1-propenyl>cyclohexanone
• 英文别名: 4,4-dimethyl-3-[(Z)-3-morpholin-4-ylprop-1-enyl]cyclohexan-1-one
• CAS: 144758-40-7
• 化学式: C₁₅H₂₅NO₂
• 分子量: 251.369
• InChiKey: UTDCMJOYCQEUJO-ARJAWSKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  4-丙炔-1-吗啉 在 sodium hydroxide 、 碲化氢 、 sodium tetrahydroborate 、 n-Bu(2-Th)Cu(CN)Li₂ 作用下， 以 四氢呋喃 、 乙醇 、 水 为溶剂， 反应 41.33h， 生成 4,4-dimethyl-3-<(Z)-3-(N-morpholino)-1-propenyl>cyclohexanone
  参考文献：
  名称：

  Tellurium in Organic Synthesis. Preparation of Z-Vinylic Cuprates from Z-Vinylic Tellurides and Their Reaction with Enones and Epoxides

  摘要：

  Z-Vinylic tellurides, obtained with 100% stereoselectivity by the hydrotelluration of acetylenes, are easily transformed into Z-vinylic higher order cyanocuprates by reaction with preformed Me(2)Cu(CN)Li-2, n-Bu(2)Cu(CN)Li-2, or n-Bu(2-Th)Cu(CN)Li-2, with total retention of the double-bond configuration. The resulting vinylic higher order cyanocuprates react with unhindered enones to give the corresponding 1,4-addition products in good yields. Reaction of the vinylic higher order cyanocuprates with monosubstituted epoxides at 0 degrees C gives the homoallylic alcohols resulting from the attack to the less-substituted carbon atom, while the disubstituted epoxides failed to react. Allylic epoxides react at -78 degrees C with the vinylic higher order cyanocuprates to give mixtures of 1,2- and 1,4-opening products, the 1,4-product predominating. In all cases the double-bond configuration of the original vinylic telluride was preserved. The vinylic cuprates derived from simple vinylic tellurides and conjugated 1-telluroenynes react with epoxides at 0 degrees C, while vinylic cuprates derived from conjugated 1-tellurodienes required the addition of 1 equiv of BF3 . Et(2)O to give the homoallylic alcohols on reaction with epoxides. The opening of optically pure epoxides through tellurium/copper transmetalation is stereospecific, giving one single stereoisomer of the corresponding homoallylic alcohol.

  DOI：

  10.1021/jo951547c

文献信息

• Higher order vinyl cyanocuprates from vinylic tellurides
  作者：Fábio C. Tucci、André Chieffi、João V. Comasseto

  DOI：10.1016/0040-4039(92)89015-5

  日期：1992.9

  Bis-vinylic tellurides, 1-tellurodienes, 1-telluroenynes and vinyl thienyl tellurides react with higher order cyanocuprates giving the corresponding higher order vinyl cyanocuprates with retention of the olefine geometry.
• Tellurium in Organic Synthesis. Preparation of <i>Z</i>-Vinylic Cuprates from <i>Z</i>-Vinylic Tellurides and Their Reaction with Enones and Epoxides
  作者：Fábio C. Tucci、André Chieffi、João V. Comasseto、Joseph P. Marino

  DOI：10.1021/jo951547c

  日期：1996.1.1

  Z-Vinylic tellurides, obtained with 100% stereoselectivity by the hydrotelluration of acetylenes, are easily transformed into Z-vinylic higher order cyanocuprates by reaction with preformed Me(2)Cu(CN)Li-2, n-Bu(2)Cu(CN)Li-2, or n-Bu(2-Th)Cu(CN)Li-2, with total retention of the double-bond configuration. The resulting vinylic higher order cyanocuprates react with unhindered enones to give the corresponding 1,4-addition products in good yields. Reaction of the vinylic higher order cyanocuprates with monosubstituted epoxides at 0 degrees C gives the homoallylic alcohols resulting from the attack to the less-substituted carbon atom, while the disubstituted epoxides failed to react. Allylic epoxides react at -78 degrees C with the vinylic higher order cyanocuprates to give mixtures of 1,2- and 1,4-opening products, the 1,4-product predominating. In all cases the double-bond configuration of the original vinylic telluride was preserved. The vinylic cuprates derived from simple vinylic tellurides and conjugated 1-telluroenynes react with epoxides at 0 degrees C, while vinylic cuprates derived from conjugated 1-tellurodienes required the addition of 1 equiv of BF3 . Et(2)O to give the homoallylic alcohols on reaction with epoxides. The opening of optically pure epoxides through tellurium/copper transmetalation is stereospecific, giving one single stereoisomer of the corresponding homoallylic alcohol.