Spiro<8-endo-methylbicyclo<4.2.0>oct-2-ene-7,2'-(1',3'-dioxolane)>

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Spiro<8-endo-methylbicyclo<4.2.0>oct-2-ene-7,2'-(1',3'-dioxolane)>
• 英文别名: Spiro[8-endo-methylbicyclo[4.2.0]oct-2-ene-7,2'-(1',3'-dioxolane)]；(1'R,6'R,8'S)-8'-methylspiro[1,3-dioxolane-2,7'-bicyclo[4.2.0]oct-2-ene]
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: AKHNEQGJSIELGA-IVZWLZJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  Spiro<8-endo-methylbicyclo<4.2.0>oct-2-ene-7,2'-(1',3'-dioxolane)> 在 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 硫酸 、 三氟化硼乙醚 、 potassium carbonate 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 36.75h， 生成 (3'S,1R,2R,3S,6R)-2-(3'-Hydroxy-3'-cyclohexylprop-1'-ynyl)-3-hydroxy-8-endo-methylbicyclo<4.2.0>octan-7-one
  参考文献：
  名称：

  Stereochemical Consequences of 6- and 8-Substitution in Reactions of Bicyclo[4.2.0]octan-7-ones

  摘要：

  Reduction (zinc/copper couple) of each epimer of 8-chloro-8-methylbicyclo[4.2.0]oct-2-en-7-one (6 and 7) gives the same product mixture containing 95% of the 8-endo-methyl compound 8. Ketalization of 8 catalyzed by TMSOTf gives the endo-methyl cyclic ethylene ketal 10 at -78-degrees-C and the exo-methyl epimer 11 (90:10) at 25-degrees-C, in contrast to beta-naphthalenesulfonic acid-catalyzed reactions. Wittig olefination of both the functionalized 8-endo-and 8-exo-methyl ketones gives only the 8-endo-methyl olefin, whereas introduction of a 6-methoxy or 6-methyl substituent favors the 8-exo configuration. A rationale for these observations is proposed.

  DOI：

  10.1021/jo00085a031
• 作为产物：
  描述：

  (1α,6α,8α)-8-methyl-8-chlorobicyclo<4.2.0>oct-2-en-7-one 在 三氟甲磺酸三甲基硅酯 铜 、 氯化铵 、 锌 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 19.0h， 生成 Spiro<8-endo-methylbicyclo<4.2.0>oct-2-ene-7,2'-(1',3'-dioxolane)>
  参考文献：
  名称：

  Stereochemical Consequences of 6- and 8-Substitution in Reactions of Bicyclo[4.2.0]octan-7-ones

  摘要：

  Reduction (zinc/copper couple) of each epimer of 8-chloro-8-methylbicyclo[4.2.0]oct-2-en-7-one (6 and 7) gives the same product mixture containing 95% of the 8-endo-methyl compound 8. Ketalization of 8 catalyzed by TMSOTf gives the endo-methyl cyclic ethylene ketal 10 at -78-degrees-C and the exo-methyl epimer 11 (90:10) at 25-degrees-C, in contrast to beta-naphthalenesulfonic acid-catalyzed reactions. Wittig olefination of both the functionalized 8-endo-and 8-exo-methyl ketones gives only the 8-endo-methyl olefin, whereas introduction of a 6-methoxy or 6-methyl substituent favors the 8-exo configuration. A rationale for these observations is proposed.

  DOI：

  10.1021/jo00085a031

文献信息

• Stereochemical Consequences of 6- and 8-Substitution in Reactions of Bicyclo[4.2.0]octan-7-ones
  作者：Helen Y. Wu、Keith A. M. Walker、Janis T. Nelson

  DOI：10.1021/jo00085a031

  日期：1994.3

  Reduction (zinc/copper couple) of each epimer of 8-chloro-8-methylbicyclo[4.2.0]oct-2-en-7-one (6 and 7) gives the same product mixture containing 95% of the 8-endo-methyl compound 8. Ketalization of 8 catalyzed by TMSOTf gives the endo-methyl cyclic ethylene ketal 10 at -78-degrees-C and the exo-methyl epimer 11 (90:10) at 25-degrees-C, in contrast to beta-naphthalenesulfonic acid-catalyzed reactions. Wittig olefination of both the functionalized 8-endo-and 8-exo-methyl ketones gives only the 8-endo-methyl olefin, whereas introduction of a 6-methoxy or 6-methyl substituent favors the 8-exo configuration. A rationale for these observations is proposed.