methyl (1R*,2R*,11S*)-11-methyltricyclo<5.4.0.0^2,11>undeca-3,7-dien-3-yl ketone | 119986-88-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (1R*,2R*,11S*)-11-methyltricyclo<5.4.0.0^2,11>undeca-3,7-dien-3-yl ketone
• 英文别名: methyl (1R*,2R*,11S*)-11-methyltricyclo[5.4.0.0^2,11]undeca-3,7-dien-3-yl ketone；1-[(1S,2S,11R)-11-methyl-3-tricyclo[5.4.0.02,11]undeca-3,7-dienyl]ethanone
• CAS: 119986-88-8
• 化学式: C₁₄H₁₈O
• 分子量: 202.296
• InChiKey: YEBQIPLZNQZRAE-HZSPNIEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  methyl (1R*,2R*,11S*)-11-methyltricyclo<5.4.0.0^2,11>undeca-3,7-dien-3-yl ketone 在 三乙胺 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 6.5h， 生成 methyl (1R*,1aS*,8bS*)-8-(tert-butyldimethylsiloxy)-1a,3,4,4a,6,7,8b-octahydro-1-methyl-1H-1,2-<1>propan<3>ylidenebenzocyclopropacycloheptene-5-carboxylate
  参考文献：
  名称：

  Studies directed toward the total synthesis of cerorubenic acid-III. 1. Expedient construction of the tetracyclic core by oxyanionic sigmatropy

  摘要：

  A synthesis of the ABCD ring framework of cerorubenic acid-III is described. Diketone 5 was first prepared by intramolecular oxidative coupling of the dienolate 10 and then suitably desymmetrized to deliver 15b. Anionic oxy-Cope rearrangement of this intermediate resulted in construction of 18, a ketone not only having all three contiguous stereogenic centers properly established but also equipped with adequate functionality for the further elaboration of ring D. In the present effort, this thrust took the form of homologation to 21, conversion to the activated diene 22, and Diels-Alder cycloaddition to methyl acrylate at high pressure. Once it became obvious that first-formed ketone 26 greatly preferred adoption of trans stereochemistry at the ring juncture, attempts to skirt this issue were made by preparing both 29 and 32. However, these advanced intermediates proved unresponsive to conjugate reduction, and attention was therefore redirected to alternative possible means for elaboration of the eastern sector.

  DOI：

  10.1021/jo00068a019
• 作为产物：
  描述：

  3-甲基-2-环己烯-1-酮 在 吡啶 、 盐酸 、 六甲基磷酰三胺 、 4-二甲氨基吡啶 、 manganese(IV) oxide 、 氢氧化钾 、 sodium hydroxide 、 PPA 、 sodium ethanolate 、 4-甲基苯磺酸吡啶 、 三氯化铁 、 双(三甲基硅烷基)氨基钾 、 溶剂黄146 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 265.5h， 生成 methyl (1R*,2R*,11S*)-11-methyltricyclo<5.4.0.0^2,11>undeca-3,7-dien-3-yl ketone
  参考文献：
  名称：

  Studies directed toward the total synthesis of cerorubenic acid-III. 1. Expedient construction of the tetracyclic core by oxyanionic sigmatropy

  摘要：

  A synthesis of the ABCD ring framework of cerorubenic acid-III is described. Diketone 5 was first prepared by intramolecular oxidative coupling of the dienolate 10 and then suitably desymmetrized to deliver 15b. Anionic oxy-Cope rearrangement of this intermediate resulted in construction of 18, a ketone not only having all three contiguous stereogenic centers properly established but also equipped with adequate functionality for the further elaboration of ring D. In the present effort, this thrust took the form of homologation to 21, conversion to the activated diene 22, and Diels-Alder cycloaddition to methyl acrylate at high pressure. Once it became obvious that first-formed ketone 26 greatly preferred adoption of trans stereochemistry at the ring juncture, attempts to skirt this issue were made by preparing both 29 and 32. However, these advanced intermediates proved unresponsive to conjugate reduction, and attention was therefore redirected to alternative possible means for elaboration of the eastern sector.

  DOI：

  10.1021/jo00068a019

文献信息

• Rapid construction of the tetracyclic nucleus of cerorubenic acid-III by oxyanionic cope chemistry
  作者：Leo A. Paquette、Marc-André Poupart

  DOI：10.1016/s0040-4039(00)80072-6

  日期：1988.1

  Ketone 3, produced directly by anionic oxy-Cope rearrangement of 4, was crafted into silyloxydiene 8, Diels-Alder condensation of which with methyl acrylate under high pressure permitted arrival at 2, a tetracyclic precursor to cerorubenic acid-III.

  酮3，通过阴离子直接产生氧应对的重排4，被制作成silyloxydiene 8，第尔斯-阿尔德缩合，其在高压下与丙烯酸甲酯在到达允许2，四环前体cerorubenic酸III。