methyl (1S,2R,4S,6S)-1,4-dimethyl-11-methylene-10-oxotricyclo<6.3.0.0^2,6>undec-8-ene-5-carboxylate | 85799-04-8

• 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 (1S,2R,4S,6S)-1,4-dimethyl-11-methylene-10-oxotricyclo<6.3.0.0^2,6>undec-8-ene-5-carboxylate
• 英文别名: methyl [2S-(2α,3aα,3bβ,7aα)]-2,3,3a,3b,4,5,7,7a-octahydro-2,3b-dimethyl-4-methylene-5-oxo-1H-cyclopenta[a]pentalene-2-carboxylate；methyl (3aS,3bR,5S,6aS)-3a,5-dimethyl-3-methylidene-2-oxo-4,6,6a,7-tetrahydro-3bH-cyclopenta[a]pentalene-5-carboxylate
• CAS: 85799-04-8
• 化学式: C₁₆H₂₀O₃
• 分子量: 260.333
• InChiKey: SEPMSEPTNLHCRD-KVFNFIISSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (1S,2R,4S,6S)-1,4-dimethyl-11-methylene-10-oxotricyclo<6.3.0.0^2,6>undec-8-ene-5-carboxylate 在 sodium hydroxide 、 sodium tetrahydroborate 、 双氧水 、 lithium iodide 作用下， 以 甲醇 、 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 36.17h， 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：

  A total synthesis of(+)-hirsutic acid.

  摘要：

  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。

  DOI：

  10.1248/cpb.38.3230
• 作为产物：
  描述：

  methyl (1R,2aR,2bR,2cR,4S,5aR,5bS,5cS)-1-(benzoyloxy)-decahydro-4,5b-dimethyl-2-oxo-1H-cyclopenta[a]cyclopropa[cd]pentalene-4-carboxylate 在 sodium periodate 、 samarium diiodide 、 对甲苯磺酸 、 苯乙酮 、 lithium diisopropyl amide 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 水 、 二甲基亚砜 、 丙酮 、 甲苯 为溶剂， 反应 111.42h， 生成 methyl (1S,2R,4S,6S)-1,4-dimethyl-11-methylene-10-oxotricyclo<6.3.0.0^2,6>undec-8-ene-5-carboxylate
  参考文献：
  名称：

  Chemoenzymatic total syntheses of the linear triquinane-type natural products (+)-hirsutic acid and (−)-complicatic acid from toluene

  摘要：

  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.

  DOI：

  10.1016/j.tet.2007.03.073

文献信息

• 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。
• A simple, highly stereocontrolled total synthesis of (+)-hirsutic acid
  作者：Masakatsu Shibasaki、Mayumi Yamazaki、Katsuhiko Iseki、Shiro Ikegami

  DOI：10.1016/s0040-4039(00)85826-8

  日期：——

  A chirally directed total synthesis of (+)-hirsutic acid from 1,3-cyclooctadiene has been accomplished in a highly stereocontrolled manner.

  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。
• Formal total synthesis of (±)-hirsutic acid C using the tandem Rh(I)-catalyzed [(5+2)+1] cycloaddition/aldol reaction
  作者：Changxia Yuan、Lei Jiao、Zhi-Xiang Yu

  DOI：10.1016/j.tetlet.2010.08.028

  日期：2010.10

  A concise formal total synthesis of the linear triquinane natural product (±)-hirsutic acid C has been achieved. This synthesis features a tandem Rh(I)-catalyzed [(5+2)+1] cycloaddition/aldol reaction as the key step to build the triquinane skeleton.

  线性三喹烷天然产物（±）-次硫酸C的简明形式全合成已实现。该合成的特征是串联Rh（I）催化的[（5 + 2）+1]环加成反应/醛醇缩合反应是构建三喹烷骨架的关键步骤。
• Total synthesis of hirsutic acid C and complicatic acid
  作者：Paul Francis Schuda、Jennifer L. Phillips、Tina M. Morgan

  DOI：10.1021/jo00364a023

  日期：1986.7
• NISHIDA, MAYUMI;ISEKI, KATSUHIKO;SHIBASAKI, MASAKATSU;IKEGAMI, SHIRO, CHEM. AND PHARM. BULL., 38,(1990) N2, C. 3230-3237
  作者：NISHIDA, MAYUMI、ISEKI, KATSUHIKO、SHIBASAKI, MASAKATSU、IKEGAMI, SHIRO

  DOI：——

  日期：——