4-(Hydroxymethyl)-2-methyl-5-methylene-3-(1-methylethyl)-2-cyclopenten-1-one | 162292-97-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-(Hydroxymethyl)-2-methyl-5-methylene-3-(1-methylethyl)-2-cyclopenten-1-one
• 英文别名: 4-(Hydroxymethyl)-2-methyl-5-methylidene-3-propan-2-ylcyclopent-2-en-1-one
• CAS: 162292-97-9
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: WWFATYSMCNXERE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 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-methyl-5-methylene-3-(1-methylethyl)-2-cyclopenten-1-one 在 jones reagent 作用下， 以 乙醚 、 丙酮 为溶剂， 反应 0.75h， 生成 3-Methyl-5-methylene-2-(1-methylethyl)-4-oxo-2-cyclopentene-1-carboxylic acid methyl ester
  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
• 作为产物：
  描述：

  4-异丙基-3-甲基-5,6-二氢-2H-吡喃-2-酮 在 4-二甲氨基吡啶 、 manganese(IV) oxide 、 lithium aluminium tetrahydride 、 正丁基锂 、 三苯基甲烷 、 氢氟酸 、 三乙胺 、 1,2-环氧辛烷 、 天然维生素E 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 1,2-二氯乙烷 、 乙腈 为溶剂， 反应 98.75h， 生成 4-(Hydroxymethyl)-2-methyl-5-methylene-3-(1-methylethyl)-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

• Total synthesis of (±)-xanthocidin using FeCl3-mediated Nazarov reaction
  作者：Kentaro Yaji、Mitsuru Shindo

  DOI：10.1016/j.tet.2010.10.084

  日期：2010.12

  The total synthesis of the antibiotic, (±)-xanthocidin (1), is described. The FeCl3-promoted fast Nazarov reaction of the β-alkoxy divinyl ketone in the presence of t-BuOH provided the α-exo-methylene cyclopentenone, which is the core skeleton of this natural product. After methoxymethyl (MOM) esterification and protection of the reactive exo-methylene unit with a phenylseleno group, dihydroxylation

  描述了抗生素（±）-黄药素（1）的总合成。在叔丁醇的存在下，FeCl 3促进了β-烷氧基二乙烯基酮的快速Nazarov反应，从而提供了α- exo-亚甲基环戊烯酮，这是该天然产物的核心骨架。在甲氧基甲基（MOM）酯化并用苯基硒烯基保护反应性外-亚甲基单元后，进行二羟基化，然后氧化，得到了黄原素MOM酯。最后，在温和条件下将该酯转化为（±）-黄药素（1）。