(3aR,4R,4aR,7aR,8S,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 | 914088-99-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aR,4R,4aR,7aR,8S,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,4R,4aR,7aR,8S,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；(4R,4aR,7aR,8S,8aS)-2,2,4-trimethyl-3a,4,4a,6,7,7a,8,8a-octahydro-5H-4,8-ethenoindeno[5,6-d][1,3]dioxol-5-one；(1S,2S,6R,7R,8R,12R)-4,4,7-trimethyl-3,5-dioxatetracyclo[5.5.2.02,6.08,12]tetradec-13-en-9-one
• CAS: 914088-99-6
• 化学式: C₁₅H₂₀O₃
• 分子量: 248.322
• InChiKey: IJOQADRYDIVESW-LXVMNVLHSA-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,4R,4aR,7aR,8S,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 hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 methyl (3aR,4R,4aR,6S,7aR,8S,8aS)-3a,4a,5,6,7,7a,8,8a-octahydro-2,2,4,6-tetramethyl-5-oxo-4,8-etheno-4H-indeno[5,6-d][1,3]dioxole-6-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
• 作为产物：
  描述：

  2-环戊烯酮 、 (3aR,7aS)-2,2,4-trimethyl-3a,7a-dihydro-1,3-benzodioxole 以73%的产率得到(3aR,4R,4aR,7aR,8S,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：

  The Chemoenzymatic Total Synthesis of Phellodonic Acid, a Biologically Active and Highly Functionalized Hirsutane Derivative Isolated from the Tasmanian Fungus Phellodon melaleucus

  摘要：

  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。

  DOI：

  10.1071/ch07403

文献信息

• The Synthesis, Structural Characterisation, and Chemoselective Manipulation of Certain Functionalised Cyclic Sulfates Derived from Chiral, Non-Racemic, and Polysubstituted Bicyclo[2.2.2]octane-2,3-diols
  作者：Martin G. Banwell、Antony L. Crisp、BoRa Lee、Ping Lan、Hannah E. Bollard、Jas S. Ward、Anthony C. Willis

  DOI：10.1071/ch21140

  日期：——

  Certain cyclic sulfates (e.g. 23) together with various of their precursor sulfites (e.g. 21 and 22) have been prepared from the corresponding chiral, non-racemic bicyclo[2.2.2]octane-2,3-diols (e.g. 20). Such diols are obtained by engaging the corresponding enzymatically derived and enantiomerically enriched or homochiral cis-1,2-dihydrocatechol (e.g. 10) or certain derivatives in either inter- or

  某些环状硫酸盐（例如23）及其各种前体亚硫酸盐（例如21和22）已从相应的手性、非外消旋双环 [2.2.2] 辛烷-2,3-二醇（例如20）制备。这种二醇是通过在分子间或分子内 Diels-Alder 环加成反应中加入相应的酶衍生和对映体富集或同手性顺式-1,2-二氢邻苯二酚（例如10）或某些衍生物而获得的。标题化合物中存在的其他官能团可以进行化学选择性操作，而不会对相关的硫酸盐残基产生不利影响。
• A chemoenzymatic total synthesis of the hirsutene-type sesquiterpene (+)-connatusin B from toluene
  作者：David J.-Y.D. Bon、Martin G. Banwell、Anthony C. Willis

  DOI：10.1016/j.tet.2010.07.059

  日期：2010.9

  The first total synthesis of the hirsutene-type sesquiterpenoid natural product (+)-connatusin B (2) is reported. The cis-1,2-dihydrocatechol 3, which is obtained in enantiomerically pure form via the enzymatic dihydroxylation of toluene, served as the starting material. Diels-Alder cycloaddition and oxa-di-pi-methane rearrangement reactions represent key chemical steps in the reaction sequence leading to the cyclopropane ring-fused linear triquinane 14. Reductive cleavage of the three-membered ring within this framework and various functional group interconversions then provide the title compound 2. (C) 2010 Elsevier Ltd. All rights reserved.
• 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。
• 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.