(5S,3E)-5,6-O-cyclohexylidene-hex-3-en-2-one | 153186-36-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (5S,3E)-5,6-O-cyclohexylidene-hex-3-en-2-one
• 英文别名: (E)-4-[(3S)-1,4-dioxaspiro[4.5]decan-3-yl]but-3-en-2-one
• CAS: 153186-36-8
• 化学式: C₁₂H₁₈O₃
• 分子量: 210.273
• InChiKey: NYYVFETWCAFIJD-QRGHLMKCSA-N

物化性质

• 沸点：
  346.9±27.0 °C(predicted)
• 密度：
  1.08±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (5S,3E)-5,6-O-cyclohexylidene-hex-3-en-2-one 在 silver(I) acetate 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 6.17h， 生成 Ethyl (1R,3S,3aR,7S,7aR)-7-hydroxy-4-methoxy-4-methyl-3-phenyloctahydropyrano<3,4-c>pyrrole-1-carboxylate
  参考文献：
  名称：

  Polyfunctionalized Pyrrolidines by Stereoselective 1,3-Dipolar Cycloaddition of Azomethine Ylides to Chiral Enones

  摘要：

  The cycloaddition reactions of chiral alpha,beta-unsaturated ketones substituted by alkoxy or amino groups in the gamma-position to azomethine ylides (obtained from glycine imines) were investigated in the presence of a base, LiBr and AgOAc. High regioselectivities were observed in most cases, resulting in the formation of a single diastereomer, particularly if a DBU/AgOAc catalyst system was employed. The influence of reaction conditions and olefin structure on the stereoselectivity of the reaction was investigated, and models rationalizing stereocontrol are proposed. In addition, an interesting deconjugation reaction of acetals derived from gamma,delta-dihydroxy alpha,beta-unsaturated enones or esters is described.

  DOI：

  10.1021/jo00121a019
• 作为产物：
  描述：

  (R)-1,4-二氧杂螺[4,5]癸烷-2-甲醛 、 1-三苯基膦-2-丙酮 以 Petroleum ether 、 苯 为溶剂， 反应 24.0h， 以4%的产率得到(5S,3Z)-5,6-O-cyclohexylidene-hex-3-en-2-one
  参考文献：
  名称：

  重氮化合物与烯酮的环加成的非对面选择性

  摘要：

  手性α，β不饱和γ -烷氧基或γ氨基酮（烯酮）1用在以立体选择性方式重氮化合物，得到偶联反应Δ 2 -pyrazolines 5和6。在所有情况下SYN -选择性环加成进行了观察。在较低的温度下，非对映异构体比例有所提高，但是没有观察到高压的显着影响。用相同的烯酮1的（E）和（Z）衍生物进行该反应，得到相同的产物。

  DOI：

  10.1016/0040-4020(94)01049-6

文献信息

• Synthesis of enantiomerically pure pyrrolidines by stereospecific cycloaddition of azomethine ylides with enones
  作者：M. Pätzel、G. Galley、P.G. Jones、A. Chrapkowsky

  DOI：10.1016/s0040-4039(00)73839-1

  日期：1993.9

  alkoxy or amino substituent in γ-position react with azomethine ylides 3 (obtained from glycine imines) in the presence of DBU/AgOAc giving enantiomerically pure pyrrolidine derivatives 4 in a stereospecific manner.

  在DBU / AgOAc的存在下，几种在γ位带有手性烷氧基或氨基取代基的（E）-α，β-不饱和酮（烯酮）2与偶氮甲亚胺3（由甘氨酸亚胺获得）反应，得到对映体纯的吡咯烷衍生物4以立体定向的方式。
• Diastereoselective 1,3-dipolar cycloaddition of nitrilimines to γ-oxygenated α,β-unsaturated enones and esters
  作者：Lutz Grubert、Guido Galley、Michael Pätzel

  DOI：10.1016/0957-4166(96)00119-x

  日期：1996.4

  stereochemical outcome of the 1,3-dipolar cycloaddition of nitrilimines to γ-oxygenated α,β-unsaturated enones and esters was investigated. By means of X-ray and NMR analysis the main diastereomers were assigned as the syn-derivatives. Novel enantiomerically pure nitrilimines were included in the investigations but did not influence the stereochemical course of the cycloaddition significantly.

  研究了亚硝胺的1,3-偶极环加成反应生成γ-氧化的α，β-不饱和烯酮和酯的立体化学结果。通过X射线和NMR分析，将主要的非对映异构体指定为顺式衍生物。新型对映体纯的亚硝胺被包括在研究中，但对环加成反应的立体化学过程没有明显影响。
• Polyfunctionalized Pyrrolidines by Stereoselective 1,3-Dipolar Cycloaddition of Azomethine Ylides to Chiral Enones
  作者：Guido Galley、Juergen Liebscher、Michael Paetzel

  DOI：10.1021/jo00121a019

  日期：1995.8

  The cycloaddition reactions of chiral alpha,beta-unsaturated ketones substituted by alkoxy or amino groups in the gamma-position to azomethine ylides (obtained from glycine imines) were investigated in the presence of a base, LiBr and AgOAc. High regioselectivities were observed in most cases, resulting in the formation of a single diastereomer, particularly if a DBU/AgOAc catalyst system was employed. The influence of reaction conditions and olefin structure on the stereoselectivity of the reaction was investigated, and models rationalizing stereocontrol are proposed. In addition, an interesting deconjugation reaction of acetals derived from gamma,delta-dihydroxy alpha,beta-unsaturated enones or esters is described.
• Diastereofacial selectivity of the cycloaddition of diazo compounds to enones
  作者：G Galley、M Pätzel、P.G Jones

  DOI：10.1016/0040-4020(94)01049-6

  日期：1995.2

  Chiral α,β-unsaturated γ-alkoxy- or γ-amino-ketones (enones) 1 react with diazo compounds in a stereoselective manner affording conjugated Δ2-pyrazolines 5 and 6. In all cases syn-selectivity for the cycloaddition was observed. The diastereomeric ratio is improved at lower temperatures, but no significant influence of high pressure is observed. Carrying out this reaction with (E) and (Z) derivatives

  手性α，β不饱和γ -烷氧基或γ氨基酮（烯酮）1用在以立体选择性方式重氮化合物，得到偶联反应Δ 2 -pyrazolines 5和6。在所有情况下SYN -选择性环加成进行了观察。在较低的温度下，非对映异构体比例有所提高，但是没有观察到高压的显着影响。用相同的烯酮1的（E）和（Z）衍生物进行该反应，得到相同的产物。