4-carboxy-2,3-dimethyl-5-methylene-2-cyclopentenone | 74216-80-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-carboxy-2,3-dimethyl-5-methylene-2-cyclopentenone
• 英文别名: (+/-)-desepoxy-4,5-didehydromethylenomycin A；Desepoxy-4,5-didehydromethylenomycin A；2,3-Dimethyl-5-methylene-4-oxo-2-cyclopentene-1-carboxylic acid；2,3-dimethyl-5-methylidene-4-oxocyclopent-2-ene-1-carboxylic acid
• CAS: 74216-80-1
• 化学式: C₉H₁₀O₃
• 分子量: 166.177
• InChiKey: YVQOPMVVZGYOBC-UHFFFAOYSA-N

物化性质

• 沸点：
  329.7±42.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 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 、 jones reagent 、 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 、 丙酮 、 乙腈 为溶剂， 反应 36.25h， 生成 4-carboxy-2,3-dimethyl-5-methylene-2-cyclopentenone
  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

• A convenient synthesis method for methylenomycin B and its application to methylenomycis A.
  作者：Kennosuke TONARI、Kozo MACHIYA、Itsuo ICHIMOTO、Hiroo UEDA

  DOI：10.1271/bbb1961.45.295

  日期：——

  A convenient synthesis method for methylenomycin B and its homolog, methylenomycin A, has been developed. Methylenomycin B, 2, 3-dimethyl-5-methylene-2-cyclopentenone (3) was synthesized: i) by methylation of Mannich derivative prepared from morpholine and 2, 3-dimethyl-2-cyclopentenone (5) or ii) by treatment of formalin with sodio derivatives of 2, 3-dimethyl-5-formyl-2-cyclopentenone (7a) and 2, 3-dimethyl-5-ethoxalyl-2-cyclopentenone (7b), both of which were easily prepared from 5 and ethyl formate or ethyl oxalate. 2, 3-Dimethyl-2, 3-epoxy-5- methylenecyclopentanone (2) was similarly prepared from the epoxide compound of 5 and ethyl oxalate. The bioassay of methylenomycin B and its related compounds against bacteria (B. subtilis, S. aureus, Ps. aeruginosa and E. coli) was also conducted. Methylenomycin A (1) and its desepoxy compound (17) were also prepared from 4-carboxy-2, 3-dimethyl-2-cyclopentenone (15) in the same procedure as described above.

  开发了一种方便的合成方法用于合成美克霉素B及其同源物美克霉素A。美克霉素B，即2, 3-二甲基-5-亚甲基-2-环戊烯酮（3），可以通过以下两种方式合成：i）通过对由莫尔菲林和2, 3-二甲基-2-环戊烯酮（5）制备的曼尼希衍生物进行甲基化，或ii）通过处理福尔马林与2, 3-二甲基-5-醛基-2-环戊烯酮（7a）和2, 3-二甲基-5-乙氧基-2-环戊烯酮（7b）的钠衍生物，这两者均可轻易地由5和乙酸乙酯或乙氧基乙酸制备而成。2, 3-二甲基-2, 3-环氧-5-亚甲基环戊酮（2）则通过5的环氧化合物与乙氧基乙酸的反应类似合成。还进行了美克霉素B及其相关化合物对细菌（枯草芽孢杆菌、金黄色葡萄球菌、绿脓杆菌和大肠杆菌）的生物测定。同时，美克霉素A（1）及其去环氧化合物（17）也采用与上述相同的方法从4-羧基-2, 3-二甲基-2-环戊烯酮（15）中制备而成。
• Synthesis of (±)-desepoxy-4,5-didehydromethylenomycin A
  作者：Masato Koreeda、Y.P.Liang Chen

  DOI：10.1016/0040-4039(81)80028-7

  日期：1981.1

  An efficient and regiochemically controlled synthesis of (±)-desepoxy-4,5-didehydromethylenomycin A is reported.

  报道了一种有效的和区域化学控制的（±）-去氧-4,5-二氢甲基松香霉素A的合成方法。
• Total synthesis of (±)-desepoxy-4,5-didehybromethylenomycin A
  作者：Diane Boschelli、Robert M. Scarborough、Amos B. Smith

  DOI：10.1016/0040-4039(81)80029-9

  日期：1981.1

  The total synthesis of (±)-desepoxy-4,5-didehydromethylenomycin A employing a retrolactonization strategy has been achieved.

  已经实现了采用逆内酯化策略的（±）-脱环氧-4,5-二氢甲基松香霉素A的全合成。
• Processes and host cells for genome, pathway, and biomolecular engineering
  申请人：enEvolv, Inc.

  公开号：US10370654B2

  公开（公告）日：2019-08-06

  The present disclosure provides compositions and methods for genomic engineering.

  本公开提供了基因组工程的组合物和方法。
• 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