4-[(tert-butyldimethylsilyl)oxy]-1-vinylcyclohexene | 216392-10-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 4-[(tert-butyldimethylsilyl)oxy]-1-vinylcyclohexene
• 英文别名: 4-tert-butyldimethylsiloxy-1-vinylcyclohex-1-ene；Tert-butyl-(4-ethenylcyclohex-3-en-1-yl)oxy-dimethylsilane
• CAS: 216392-10-8
• 化学式: C₁₄H₂₆OSi
• 分子量: 238.445
• InChiKey: LSIJUFAINZVKFJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.67
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-[(tert-butyldimethylsilyl)oxy]-1-vinylcyclohexene 在 氢氟酸 作用下， 以 乙腈 为溶剂， 反应 0.33h， 以91%的产率得到4-vinyl-3-cyclohexenol
  参考文献：
  名称：

  Enantioselective Diels−Alder Cycloadditions with (SS)-2-(p-Tolylsulfinyl)-1,4-naphthoquinone:  Efficient Kinetic Resolution of Chiral Racemic Vinylcyclohexenes

  摘要：

  Chiral racemic vinylcyclohexenes 1a-m, bearing allylic and nonallylic oxygenated substituents on the cyclohexene ring, were submitted to Diels-Alder reactions with enantiomerically pure (SS)(2-p-tolylsulfinyl)-1,4-naphthoquinone. The tandem cycloaddition/pyrolytic sulfoxide elimination led to the formation of enantiomerically enriched angularly tetracyclic quinones (+)-8a and (+)-12, arising from the kinetic resolution of the racemic diene. Dienes la-c, bearing an alkoxy substituent at the allylic position C-3, and 1d-g, with C-3 alkoxy and C-5 methyl groups, gave exclusively quinones (+)-8a-g, resulting from the anti approach to the dienophile. A similar anti selectivity occurred in cycloadditions of dienes 1ij, viith the alkoxy group situated at the allylic position C-6. Nonallylic 4-substituted vinylcyclohexenes 1k-m evolved to ca. 75:25 mixtures of (+)-anti-8k-m and (+)-syn-12k-m derivatives. In all cases, (SS)-(2-p-tolylsulfinyl)-1,4-naphthoquinone reacted from the less hindered face of the more reactive s-cis conformation, giving rise to products in moderate to excellent enantiomeric excesses. Steric effects and torsional interactions in the corresponding approaches account for the observed pi-facial diastereoselectivities at both partners.

  DOI：

  10.1021/jo9811874
• 作为产物：
  描述：

  4-羟基环己酮乙二醇缩醛 在 四(三苯基膦)钯 咪唑 、 cerium(III) chloride 、 双(三甲基硅烷基)氨基钾 、 sodium iodide 、 lithium chloride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 19.0h， 生成 4-[(tert-butyldimethylsilyl)oxy]-1-vinylcyclohexene
  参考文献：
  名称：

  Enantioselective Diels−Alder Cycloadditions with (SS)-2-(p-Tolylsulfinyl)-1,4-naphthoquinone:  Efficient Kinetic Resolution of Chiral Racemic Vinylcyclohexenes

  摘要：

  Chiral racemic vinylcyclohexenes 1a-m, bearing allylic and nonallylic oxygenated substituents on the cyclohexene ring, were submitted to Diels-Alder reactions with enantiomerically pure (SS)(2-p-tolylsulfinyl)-1,4-naphthoquinone. The tandem cycloaddition/pyrolytic sulfoxide elimination led to the formation of enantiomerically enriched angularly tetracyclic quinones (+)-8a and (+)-12, arising from the kinetic resolution of the racemic diene. Dienes la-c, bearing an alkoxy substituent at the allylic position C-3, and 1d-g, with C-3 alkoxy and C-5 methyl groups, gave exclusively quinones (+)-8a-g, resulting from the anti approach to the dienophile. A similar anti selectivity occurred in cycloadditions of dienes 1ij, viith the alkoxy group situated at the allylic position C-6. Nonallylic 4-substituted vinylcyclohexenes 1k-m evolved to ca. 75:25 mixtures of (+)-anti-8k-m and (+)-syn-12k-m derivatives. In all cases, (SS)-(2-p-tolylsulfinyl)-1,4-naphthoquinone reacted from the less hindered face of the more reactive s-cis conformation, giving rise to products in moderate to excellent enantiomeric excesses. Steric effects and torsional interactions in the corresponding approaches account for the observed pi-facial diastereoselectivities at both partners.

  DOI：

  10.1021/jo9811874

文献信息

• Synthesis of 2-Ene-1,4-diols by a New Cascade-Opening of 1,3-Diepoxides: Towards an Efficient Synthesis of Dihydroxytaxoid Derivatives
  作者：María J. Aldegunde、Luis Castedo、Juan R. Granja

  DOI：10.1002/chem.200802621

  日期：2009.5.4

  Taxing taxanes: A new method for the preparation of alk‐2‐ene‐1,4‐diols from 1,3‐dienes, especially for geometrical constrained derivatives, via dioxirane derivative formation followed by TiIII‐induced oxirane ring opening, is described. The strategy has been very efficiently implemented to the construction of the 11‐ene‐10,13‐diol moiety present in taxol derivatives.

  课税紫杉烷类：描述了一种新的方法，该方法可通过由二环氧乙烷衍生物形成，然后由Ti III诱导的环氧乙烷开环，从1,3-二烯制备烷基-2-烯-1,4-二醇，特别是对于几何受限的衍生物。。该策略已非常有效地实施，以构建紫杉醇衍生物中存在的11-ene-10,13-二醇部分。
• Enantioselective Diels−Alder Cycloadditions with (S<i>S</i>)-2-(<i>p-</i>Tolylsulfinyl)-1,4-naphthoquinone:  Efficient Kinetic Resolution of Chiral Racemic Vinylcyclohexenes
  作者：M. Carmen Carreño、Antonio Urbano、Claudio Di Vitta

  DOI：10.1021/jo9811874

  日期：1998.11.1

  Chiral racemic vinylcyclohexenes 1a-m, bearing allylic and nonallylic oxygenated substituents on the cyclohexene ring, were submitted to Diels-Alder reactions with enantiomerically pure (SS)(2-p-tolylsulfinyl)-1,4-naphthoquinone. The tandem cycloaddition/pyrolytic sulfoxide elimination led to the formation of enantiomerically enriched angularly tetracyclic quinones (+)-8a and (+)-12, arising from the kinetic resolution of the racemic diene. Dienes la-c, bearing an alkoxy substituent at the allylic position C-3, and 1d-g, with C-3 alkoxy and C-5 methyl groups, gave exclusively quinones (+)-8a-g, resulting from the anti approach to the dienophile. A similar anti selectivity occurred in cycloadditions of dienes 1ij, viith the alkoxy group situated at the allylic position C-6. Nonallylic 4-substituted vinylcyclohexenes 1k-m evolved to ca. 75:25 mixtures of (+)-anti-8k-m and (+)-syn-12k-m derivatives. In all cases, (SS)-(2-p-tolylsulfinyl)-1,4-naphthoquinone reacted from the less hindered face of the more reactive s-cis conformation, giving rise to products in moderate to excellent enantiomeric excesses. Steric effects and torsional interactions in the corresponding approaches account for the observed pi-facial diastereoselectivities at both partners.