methyl (2R*,3aS*,3bR*,7aR*)-2,3,3a,3b,4,5,7,7a-octahydro-2,3b-dimethyl-5-oxo-1H-cyclopentapentalene-2-carboxylate | 70004-11-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl (2R*,3aS*,3bR*,7aR*)-2,3,3a,3b,4,5,7,7a-octahydro-2,3b-dimethyl-5-oxo-1H-cyclopentapentalene-2-carboxylate
• 英文别名: 1,4-dimethyl-4-carbomethoxytricyclo[6.3.0.0^2,6]undec-8-en-10-one；methyl (3aS,3bR,5S,6aS)-3a,5-dimethyl-2-oxo-3,3b,4,6,6a,7-hexahydrocyclopenta[a]pentalene-5-carboxylate
• CAS: 70004-11-4
• 化学式: C₁₅H₂₀O₃
• 分子量: 248.322
• InChiKey: PMIDPXPGYHERDV-VFGSGVCASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

上下游信息

反应信息

• 作为反应物：
  描述：

  methyl (2R*,3aS*,3bR*,7aR*)-2,3,3a,3b,4,5,7,7a-octahydro-2,3b-dimethyl-5-oxo-1H-cyclopentapentalene-2-carboxylate 在 sodium hydroxide 、 sodium tetrahydroborate 、 双氧水 、 溶剂黄146 、 lithium iodide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 生成 (1aR-(1aalpha,2beta,3Abeta,3balpha,5alpha,6aalpha,7As*))-十氢-2-羟基-3a,5-二甲基-3-亚甲基-环戊二烯并(4,5)二并环戊烯并(1,6a-b)环氧乙烯-5-羧酸
  参考文献：
  名称：

  一种简单的，高度立体受控的（+）-亚硫酸氢钾的全合成

  摘要：

  由1,3-环辛二烯手性完全合成（+）-亚硫酸的酸已经以高度立体可控的方式完成。

  DOI：

  10.1016/s0040-4039(00)85826-8
• 作为产物：
  描述：

  tert-butyl cyclopent-3-ene-1-carboxylate 在 sodium tetrahydroborate 、 锌铜偶 、 chromium(II) perchlorate 、 lithium dimethylcuprate 、 氧气 、 palladium diacetate 、 铜 、 溶剂黄146 、 乙二胺 、 palladium dichloride 、 锌 、 lithium diisopropyl amide 、 三氯氧磷 作用下， 以 1,4-二氧六环 、 甲醇 、 乙醚 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 101.67h， 生成 methyl (2R*,3aS*,3bR*,7aR*)-2,3,3a,3b,4,5,7,7a-octahydro-2,3b-dimethyl-5-oxo-1H-cyclopentapentalene-2-carboxylate
  参考文献：
  名称：

  Iterative three-carbon annelation. A stereoselective total synthesis of (.+-.)-hirsutic acid C

  摘要：

  DOI：

  10.1021/ja00346a054

文献信息

• A short formal total synthesis of (±)-hirsutic acid
  作者：Guillaume Revol、Christian Fuchs、Samir Z. Zard

  DOI：10.1139/v2012-037

  日期：2012.11

  A short formal total synthesis of (±)-hirsutic acid is described using a Claisen rearrangement and a radical cascade as the key steps. The radical sequence involves an intermolecular addition of a radical derived from a xanthate followed by a cyclization and transfer of the xanthate group.

  本文介绍了一种简短的正式全合成(±)-hirsutic acid的方法，其中Claisen重排和自由基级联反应是关键步骤。自由基序列包括从黄酸酯中衍生出的自由基的分子间加成，随后进行环化和黄酸酯基团的转移。
• A total synthesis of(+)-hirsutic acid.
  作者：Mayumi NISHIDA、Katsuhiko ISEKI、Masakatsu SHIBASAKI、Shiro IKEGAMI

  DOI：10.1248/cpb.38.3230

  日期：——

  The first asymmetric total synthesis of (+)-hirsutic acid has been accomplished in a highly stereocontrolled manner, including a novel method for the preparation of (1S, 5R, 6S)-6-hydroxy-cis-bicyclo[3.3.0]octan-3-one and a stereospecific Simmons-Smith reaction controlled by the participation of a relatively remote hydroxyl group.

  首次以高度立体控制的方式完成了(+)-毛木酸的不对称全合成，其中包括一种制备(1S,5R,6S)-6-羟基-顺式-双环[3.3.0]辛烷的新方法-3-酮和由相对较远的羟基参与控制的立体特异性西蒙斯-史密斯反应。
• Synthesis of embellished bicyclo[2.2.2]octenones and a sigmatropic 1,2-acyl shift in an excited state: a novel and stereoselective route to (±)-hirsutic acid C and complicatic acid
  作者：Vishwakarma Singh、Dilip K. Tosh、Shaikh M. Mobin

  DOI：10.1016/j.tetlet.2003.12.095

  日期：2004.2

  Formal syntheses of hirsutic acid C and complicatic acid via cycloaddition of cyclohexa-2,4-dienone with methyl methacrylate and a triplet sensitized 1,2-acyl shift are described. The X-ray crystal structure of one of the key intermediates is also reported.

  描述了通过环己基2，4-二烯酮与甲基丙烯酸甲酯的环加成反应和三重态敏化的1，2-酰基转移而形成的水杨酸C和复杂酸的形式合成。还报道了关键中间体之一的X射线晶体结构。
• 1,2-CARBONYL TRANSPOSITION OF<i>CIS</i>-BICYCLO[3.3.O]OCTAN-2-ONE TO ITS 3-ONE SKELETON: APPLICATION TO SYNTHESES OF<i>dl</i>-HIRSUTIC ACID AND<i>dl</i>-9(0)-METHANOPROSTACYCLIN
  作者：Mayumi Yamazaki、Masakatsu Shibasaki、Shiro Ikegami

  DOI：10.1246/cl.1981.1245

  日期：1981.9.5

  A synthetic route to dl-hirsutic acid and an improved synthesis of dl-9(0)-methanoprostacyclin, both of which employ the 1,2-carbonyl transposition as a key step, are described.

  描述了 dl-毛草酸的合成路线和 dl-9(0)-methanoprostacyclin 的改进合成，这两种方法均采用 1,2-羰基转座作为关键步骤。
• Chemoenzymatic total syntheses of the linear triquinane-type natural products (+)-hirsutic acid and (−)-complicatic acid from toluene
  作者：Martin G. Banwell、Kerrie A.B. Austin、Anthony C. Willis

  DOI：10.1016/j.tet.2007.03.073

  日期：2007.7

  Total syntheses of title natural products, 1 and 2, have been achieved using the cis-1,2-dihydrocatechol 7 as starting material. Compound 7 is readily obtained in large quantity and enantiomerically pure form through the whole-cell biotransformation of toluene using the genetically engineered micro-organism Escherichia coli JM109 (pDTG601) that over-expresses the enzyme toluene dioxygenase (TDO). Three key chemical steps were employed in these syntheses, the first of which was a high-pressure- promoted Diels-Alder cycloaddition reaction between diene 8 and cyclopentenone to give adduct 9. The second key step was the photochemically promoted oxa-di-pi-methane rearrangement of the bicyclo[2.2.2] octenone derivative, 18, of 9 to give 20 while the third key step was the reductive cleavage of the last compound so as to afford the linear triquinane 22. Elaboration of compound 22 to targets 1 and 2 followed conventional and/or established procedures. Single-crystal X-ray analyses were carried out on compounds 10-13, 15, 18, 24, and 34. (c) 2007 Elsevier Ltd. All rights reserved.