4-(Hydroxymethyl)-2,3-dimethyl-5-methylene-2-cyclopenten-1-one | 162293-06-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-(Hydroxymethyl)-2,3-dimethyl-5-methylene-2-cyclopenten-1-one
• 英文别名: 4-(Hydroxymethyl)-2,3-dimethyl-5-methylidenecyclopent-2-en-1-one；4-(hydroxymethyl)-2,3-dimethyl-5-methylidenecyclopent-2-en-1-one
• CAS: 162293-06-3
• 化学式: C₉H₁₂O₂
• 分子量: 152.193
• InChiKey: ORAWUEFISRSUKX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(Hydroxymethyl)-2,3-dimethyl-5-methylene-2-cyclopenten-1-one 在 jones reagent 作用下， 以 丙酮 为溶剂， 以72%的产率得到4-carboxy-2,3-dimethyl-5-methylene-2-cyclopentenone
  参考文献：
  名称：

  Cationic cyclopentaannelation: an efficient methylenomycin synthesis

  摘要：

  DOI：

  10.1021/ja00272a045
• 作为产物：
  描述：

  (Z)-7-[tert-butyl(dimethyl)silyl]oxy-4,5-dimethylhept-4-en-1-yn-3-ol 在 manganese(IV) oxide 、 氢氟酸 、 1,2-环氧辛烷 、 天然维生素E 作用下， 以 四氢呋喃 、 二氯甲烷 、 1,2-二氯乙烷 、 乙腈 为溶剂， 反应 35.5h， 生成 4-(Hydroxymethyl)-2,3-dimethyl-5-methylene-2-cyclopenten-1-one
  参考文献：
  名称：

  Enynones in Organic Synthesis. 7. Substituent Effects on the .alpha.-Tocopherol-Catalyzed Cyclization of Enynones to Methylenecyclopentenones. Convenient Syntheses of Members of the Methylenomycin Class of Antibiotics

  摘要：

  Substituent effects on the a-tocopherol (vitamin E, 3b) catalyzed cyclization of a wide variety of enynones 1a-z to methylenecyclopentenones 7a-z have been examined, with particular emphasis given to electron-withdrawing and -donating groups at positions 2-4 and 6. In general, electron-withdrawing groups at positions 4 and 6 dramatically accelerate the cyclization process, while strong electron-donating groups at positions 3 and 4 completely inhibit reaction. Relatively little effect is exerted by groups at C-2, except for the methyl ester derivative 1i, which is totally unreactive. This methodology was employed in the syntheses of the methylenecyclopentenone antibiotics methylenomycin B (7a) and desepoxy-4,5-didehydromethylenomycin A (7z) and in formal syntheses of methylenomycin A (8) and xanthocidin (9).

  DOI：

  10.1021/jo00097a036

文献信息

• Cationic cyclopentaannelation: an efficient methylenomycin synthesis
  作者：Marcus A. Tius、Donald P. Astrab、Abdul H. Fauq、Jean Bernard. Ousset、Sanjay. Trehan

  DOI：10.1021/ja00272a045

  日期：1986.6
• Enynones in Organic Synthesis. 7. Substituent Effects on the .alpha.-Tocopherol-Catalyzed Cyclization of Enynones to Methylenecyclopentenones. Convenient Syntheses of Members of the Methylenomycin Class of Antibiotics
  作者：Peter A. Jacobi、Harry L. Brielmann、Reginald O. Cann

  DOI：10.1021/jo00097a036

  日期：1994.9

  Substituent effects on the a-tocopherol (vitamin E, 3b) catalyzed cyclization of a wide variety of enynones 1a-z to methylenecyclopentenones 7a-z have been examined, with particular emphasis given to electron-withdrawing and -donating groups at positions 2-4 and 6. In general, electron-withdrawing groups at positions 4 and 6 dramatically accelerate the cyclization process, while strong electron-donating groups at positions 3 and 4 completely inhibit reaction. Relatively little effect is exerted by groups at C-2, except for the methyl ester derivative 1i, which is totally unreactive. This methodology was employed in the syntheses of the methylenecyclopentenone antibiotics methylenomycin B (7a) and desepoxy-4,5-didehydromethylenomycin A (7z) and in formal syntheses of methylenomycin A (8) and xanthocidin (9).