(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.