3-<(Methoxymethyl)oxy>-1-vinylcyclohexene | 170508-24-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-<(Methoxymethyl)oxy>-1-vinylcyclohexene
• 英文别名: 3-[(methoxymethyl)oxy]-1-vinylcyclohexene；1-Ethenyl-3-(methoxymethoxy)cyclohexene
• CAS: 170508-24-4
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: IIRPKTJRXDHZFZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-<(Methoxymethyl)oxy>-1-vinylcyclohexene 在 氧气 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲苯 、 苯 为溶剂， 反应 8.0h， 生成 Acetic acid 1-methoxymethoxy-7,12-dioxo-1,2,3,4,7,12-hexahydro-benzo[a]anthracen-8-yl ester
  参考文献：
  名称：

  Synthetic Studies of the Angucycline Antibiotics. Stereocontrolled Assembly of the SF 2315B Ring System

  摘要：

  The stereocontrolled assembly of epoxy quinol 2 is described. Diels-Alder cycloaddition between 2-bromo-5-acetoxyjuglone (5) and 3-[(triisopropylsilyl)oxy]-1-vinylcyclohexene (6c) followed by saponification provided quinone 11b in good overall yield. Oxygenation of a tetrahydrofuran solution of 11b in the presence of tetrabutylammonium fluoride resulted in the production of epoxy alcohols alpha-12b and alpha-13b. Epoxy alcohol alpha-12b was converted to epoxy quinol 2 in five steps. A key transformation of the latter reaction sequence was a C1 hydroxyl-directed reduction of the C12 keto group (20 --> 21). The assigned structure of 2 was confirmed by single-crystal X-ray analysis.

  DOI：

  10.1021/jo00126a043
• 作为产物：
  描述：

  3-vinyl-2-cyclohexen-1-ol 、 氯甲基甲基醚 在 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 以75%的产率得到3-<(Methoxymethyl)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

• 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.
• Synthetic Studies of the Angucycline Antibiotics. Stereocontrolled Assembly of the SF 2315B Ring System
  作者：Kyungjin Kim、Yu Guo、Gary A. Sulikowski

  DOI：10.1021/jo00126a043

  日期：1995.10

  The stereocontrolled assembly of epoxy quinol 2 is described. Diels-Alder cycloaddition between 2-bromo-5-acetoxyjuglone (5) and 3-[(triisopropylsilyl)oxy]-1-vinylcyclohexene (6c) followed by saponification provided quinone 11b in good overall yield. Oxygenation of a tetrahydrofuran solution of 11b in the presence of tetrabutylammonium fluoride resulted in the production of epoxy alcohols alpha-12b and alpha-13b. Epoxy alcohol alpha-12b was converted to epoxy quinol 2 in five steps. A key transformation of the latter reaction sequence was a C1 hydroxyl-directed reduction of the C12 keto group (20 --> 21). The assigned structure of 2 was confirmed by single-crystal X-ray analysis.