(+/-)-desdihydroxy-4,5-didehydroxanthocidin | 80927-72-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-desdihydroxy-4,5-didehydroxanthocidin
• 英文别名: 3-Methyl-5-methylidene-4-oxo-2-propan-2-ylcyclopent-2-ene-1-carboxylic acid；3-methyl-5-methylidene-4-oxo-2-propan-2-ylcyclopent-2-ene-1-carboxylic acid
• CAS: 80927-72-6
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: TZYRKABFSHPLIU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-desdihydroxy-4,5-didehydroxanthocidin 在 碘代三甲硅烷 、 silver carbonate 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 8-isopropyl-7-methyl-3-oxabicyclo<3.3.0>oct-7-ene-2,6-dione
  参考文献：
  名称：

  （±）-黄药素的合成

  摘要：

  描述了（±）-黄药素（一种复杂且不稳定的环戊烷类抗生素）的有效全合成。关键的环戊烯化步骤的成功表明该反应的一般形式具有更大的通用性。

  DOI：

  10.1016/0040-4020(96)00913-1
• 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 、 jones reagent 、 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 、 丙酮 、 乙腈 为溶剂， 反应 91.5h， 生成 (+/-)-desdihydroxy-4,5-didehydroxanthocidin
  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）。
• Total synthesis of (±)-xanthocidin and (±)-desdihydroxy-4,5-dihydroxanthocidin
  作者：Diane Boschelli、Amos B. Smith

  DOI：10.1016/s0040-4039(01)82006-2

  日期：1981.1

  The first total synthesis of both (±)-xanthocidin (1), a novel α-methylene cyolopentanoid antibiotic, and (±)-desdihydroxy-4,5-dihydpoxanthocidin (2), the likely penultimate biosynthetic precursor is reported.

  据报道，新型的α-亚甲基环戊二素类抗生素（±）-黄药素（1）和可能的倒数第二个生物合成前体（±）-desdihydroxy-4,5-dihydpoxanthocidin（2）的首次全合成。
• 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
• Stereocontrolled total synthesis of (.+-.)-xanthocidin, two diastereomers, (.+-.)-epixanthocidin and (.+-.)-.beta.-isoxanthocidin, and (.+-.)-dedihydroxy-4,5-didehydroxanthocidin, a likely biosynthetic precursor
  作者：Amos B. Smith、Diane Boschelli

  DOI：10.1021/jo00156a015

  日期：1983.4
• 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).