(3aR,4S,4aS,7aS,8R,8aS)-3a,4,4a,6,7,7a,8,8a-octahydro-2,2,4-trimethyl-4,8-etheno-5H-indeno[5,6-d]-1,3-dioxol-5-one | 499121-57-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aR,4S,4aS,7aS,8R,8aS)-3a,4,4a,6,7,7a,8,8a-octahydro-2,2,4-trimethyl-4,8-etheno-5H-indeno[5,6-d]-1,3-dioxol-5-one
• 英文别名: (3aR,4S,4aS,7aS,8R,8aS)-3a,4,4a,6,7,7a,8,8a-octahydro-2,2,4-trimethyl-4,8-etheno-5H-indeno[5,6-d][1,3]dioxol-5-one；(3aR,4S,4aS,7aS,8R,8aS)-3a,4a,5,6,7,7a,8,8a-octahydro-2,2,4-trimethyl-4,8-etheno-5H-indeno[5,6-d]-1,3-dioxol-5-one；(1R,2S,6R,7S,8S,12S)-4,4,7-trimethyl-3,5-dioxatetracyclo[5.5.2.02,6.08,12]tetradec-13-en-9-one
• CAS: 499121-57-2
• 化学式: C₁₅H₂₀O₃
• 分子量: 248.322
• InChiKey: IJOQADRYDIVESW-AFGOTSJHSA-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：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3aR,4S,4aS,7aS,8R,8aS)-3a,4,4a,6,7,7a,8,8a-octahydro-2,2,4-trimethyl-4,8-etheno-5H-indeno[5,6-d]-1,3-dioxol-5-one 在 lithium aluminium tetrahydride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 33.0h， 生成 (1R,2S,6R,7S,8S,12S)-4,4,7,10,10-pentamethyl-3,5-dioxatetracyclo[5.5.2.02,6.08,12]tetradec-13-en-9-ol
  参考文献：
  名称：

  A chemoenzymatic synthesis of (−)-hirsutene from toluene

  摘要：

  通过一系列反应，包括高压促进的Diels-Alder环加成和oxa-di-π-甲烷重排步骤，从甲苯的微生物氧化得到的对映纯顺式-1,2-二醇2已经转化为三环庚烷（-）-毛壳素1。

  DOI：

  10.1039/b208778b
• 作为产物：
  描述：

  (2R,3S)-2,3-dihydroxy-1-methylcyclohexa-4,6-diene 在 对甲苯磺酸 作用下， 生成 (3aR,4S,4aS,7aS,8R,8aS)-3a,4,4a,6,7,7a,8,8a-octahydro-2,2,4-trimethyl-4,8-etheno-5H-indeno[5,6-d]-1,3-dioxol-5-one
  参考文献：
  名称：

  A Chemoenzymatic and Enantioselective Route to the Tricyclic Frameworks Associated with the Protoilludane and Marasmane Classes of Sesquiterpene

  摘要：

  对映体纯度为顺式-1,2-二氢邻苯二酚 3 是通过微生物对甲苯进行二羟基化反应而得到的，经过十个步骤（包括最初的 Diels-Alder 环加成反应），该对映体纯度为顺式-1,2-二氢邻苯二酚 3 变成了三环酮 12。直接辐照后一种化合物的苯溶液可得到化合物 13 和 14 的混合物，这两种化合物分别体现了倍半萜天然产物 tsugicoline A (1) 和 isovelleral (2) 的三环框架。

  DOI：

  10.1071/ch04131

文献信息

• The Chemoenzymatic Total Synthesis of Phellodonic Acid, a Biologically Active and Highly Functionalized Hirsutane Derivative Isolated from the Tasmanian Fungus Phellodon melaleucus
  作者：Tristan A. Reekie、Kerrie A. B. Austin、Martin G. Banwell、Anthony C. Willis

  DOI：10.1071/ch07403

  日期：——

  A total synthesis of the title natural product, 1, has been achieved using the cis-1,2-dihydrocatechol 7 as starting material. Compound 7 is readily obtained in large quantity and in an enantiomerically pure form through the whole-cell biotransformation of toluene using the genetically engineered microorganism E. coli JM109 (pDTG601) that overexpresses the enzyme toluene dioxygenase (TDO). Three key chemical steps were employed in the synthesis, the first of which was the microwave-promoted Diels–Alder cycloaddition reaction between diene 8 and cyclopent-1-en-2-one to give adduct 9. The second key step was the photochemically promoted oxa-di-π-methane rearrangement of the bicyclo[2.2.2]octenone derivative 15 of 9 to give the epimers 16 and 17, and the third key step was the reductive cleavage of the last pair of compounds so as to afford the linear triquinane 19. Elaboration of compound 19 to target 1 followed established procedures. Single-crystal X-ray analyses were carried out on compounds 11 and 19.

  以顺式-1,2-二氢邻苯二酚 7 为起始原料，实现了标题天然产物 1 的全合成。利用基因工程微生物大肠杆菌 JM109 (pDTG601)过量表达甲苯二氧 化酶（TDO），通过甲苯的全细胞生物转化，很容易获得大量对映体纯的化合物 7。合成过程中采用了三个关键化学步骤，第一个步骤是二烯 8 与环戊-1-烯-2-酮发生微波促进的 Diels-Alder 环加成反应，生成加合物 9。第二个关键步骤是光化学促进 9 的双环[2.2.2]辛烯酮衍生物 15 的氧杂-二-π-甲烷重排反应，得到外延物 16 和 17，第三个关键步骤是最后一对化合物的还原裂解，得到线性三喹啉 19。按照既定程序将化合物 19 制成目标化合物 1。对化合物 11 和 19 进行了单晶 X 射线分析。
• A chemoenzymatic synthesis of the linear triquinane (−)-hirsutene and identification of possible precursors to the naturally occurring (+)-enantiomer
  作者：Martin G Banwell、Alison J Edwards、Gwion J Harfoot、Katrina A Jolliffe

  DOI：10.1016/j.tet.2003.10.122

  日期：2004.1

  biotransformation process, has been converted over 17 steps into the linear triquinane (−)-hirsutene. Since the enantiomer of the starting material is also available this work constitutes a formal total synthesis of the naturally occurring (+)-form of hirsutene. Furthermore, minor modifications of the route used here offer the possibility of accessing (+)-hirsutene from the original starting material.

  对映体纯的顺式-1,2-二氢邻苯二酚，在全细胞生物转化过程中很容易通过甲苯双加氧酶介导的甲苯二羟基化获得，已通过17个步骤转化为线性三喹烷（-）-hirsutene。由于起始原料的对映异构体也是可用的，因此该工作构成了天然存在的hirsutene（+）-形式的正式全合成。此外，此处使用的路线的细微修改提供了从原始原料中获取（+）-hirsutenene的可能性。
• A Chemoenzymatic Total Synthesis of the Protoilludane Aryl Ester (+)-Armillarivin
  作者：Brett D. Schwartz、Eliška Matoušová、Richard White、Martin G. Banwell、Anthony C. Willis

  DOI：10.1021/ol400583c

  日期：2013.4.19

  The title natural product, 1, has been synthesized in 20 steps from the enantiomerically pure cis-1,2-dihydrocatechol 2, itself obtained through the whole-cell biotransformation of toluene. The pivotal steps in the reaction sequence involve a Diels-Alder cycloaddition reaction between diene 2 and cyclopentenone (3) and the photochemically promoted 1,3-acyl rearrangement of the bicyclo[2.2.2]oct-4-en-1-one 20 derived from the cycloadduct 4.
• 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.