3α,10α-dihydroxy-endo-anti-endo-quinone-cyclopentadiene-bisadduct | 195301-19-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3α,10α-dihydroxy-endo-anti-endo-quinone-cyclopentadiene-bisadduct
• CAS: 195301-19-0
• 化学式: C₁₆H₂₀O₂
• 分子量: 244.334
• InChiKey: SXBVEXODMXGTTI-CHATTWHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  18.0
• 可旋转键数：
  0.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  40.46
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  3α,10α-dihydroxy-endo-anti-endo-quinone-cyclopentadiene-bisadduct 在 碘 、 potassium iodide 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 6.0h， 以82%的产率得到10α-hydroxy-13β-iodo-17-oxahexacyclo<10.2.1.1^5,8.1^3,14.0^2,11.0^4,9>-6-heptadecene
  参考文献：
  名称：

  Synthesis of Dioxa-Cages as a New Probe for the Stereochemistry of the Bisadducts ofp-Quinone with Cyclopentadiene and Cyclohexadiene

  摘要：

  AbstractThe synthesis of dioxa‐cages via iodine‐induced cyclization reaction can be used as a new method for the determination of the stereochemistry of the bisadducts of p‐quinone with cyclopentadiene and cyclohexadiene. The bisadducts 2 and 8 were converted into the dioxa‐cages 13a and 13b via a three‐step sequence, respectively. The stereochemistry of 13a and 13b was determined on the basis of NOE experiments.

  DOI：

  10.1002/jccs.199800120
• 作为产物：
  描述：

  (1R,4S,4aR,5S,8R,8aS,9aS,10aR)-1,4,4a,5,8,8a,9a,10a-octahydro-1,4:5,8-dimethanoanthracene-9,10-dione 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 6.0h， 以80%的产率得到3α,10α-dihydroxy-endo-anti-endo-quinone-cyclopentadiene-bisadduct
  参考文献：
  名称：

  Synthesis of Dioxa-Cages as a New Probe for the Stereochemistry of the Bisadducts ofp-Quinone with Cyclopentadiene and Cyclohexadiene

  摘要：

  AbstractThe synthesis of dioxa‐cages via iodine‐induced cyclization reaction can be used as a new method for the determination of the stereochemistry of the bisadducts of p‐quinone with cyclopentadiene and cyclohexadiene. The bisadducts 2 and 8 were converted into the dioxa‐cages 13a and 13b via a three‐step sequence, respectively. The stereochemistry of 13a and 13b was determined on the basis of NOE experiments.

  DOI：

  10.1002/jccs.199800120

文献信息

• Alkyl radical cyclization to vinylogous carbonates for the stereoselective synthesis of unsymmetrical dioxa-cage compounds: effect of conformation on the rate of cyclization versus reduction
  作者：Santosh J. Gharpure、Suheel K. Porwal

  DOI：10.1016/j.tet.2010.11.098

  日期：2011.2

  ether linkages employing a 6-exo-trig alkyl radical cyclization to vinylogous carbonates is developed. The radical precursors are prepared from the diols obtained from the Diels–Alder adducts via iodoetherification followed by addition of the alcohol to the ethyl propiolate. The geometrical constrains play important role in deciding the outcome of the reaction as cyclization versus simple reduction

  提出了一种有效的策略，用于立体选择性地构建不对称的含醚键的二氧杂笼化合物，该化合物采用6- exo - trig烷基自由基环化成碳酸亚乙烯基酯。自由基前体是由Diels-Alder加合物中的二醇经碘醚化制得的，然后将醇加到丙酸乙酯中。几何约束在决定反应的结果方面起着重要作用，这是环化与简单还原的关系。通过5- exo - trig形成单氧杂笼化合物还描述了分子内烷基自由基环化为烯烃。二恶英笼子也可以采用串联的氧化汞分解-自由基环化成碳酸亚乙烯酯的方法，以相同的效率和减少的步骤数进行组装。
• Synthesis and catalytic reactivity of sterically and electronically modified D4-symmetric metallotetraarylporphyrins
  作者：Ronald L. Halterman、Shyi-Tai Jan、Aladamash H. Abdulwali、David J. Standlee

  DOI：10.1016/s0040-4020(97)00730-8

  日期：1997.8

  Two new sterically-modified and two electronically-modified D-4-symmetrical tetraarylporphyrin ligands have been prepared and the catalytic activity of their manganese complexes in epoxidations of aryl-substituted alkenes studied. Moderate reactivity changes were observed in catalytic epoxdiations with these electronically varied tetraaarylporphyrin complexes, the methoxy derivative giving slightly improved selectivity (83% e.e. with cis-beta-methylstyrene). (C) 1997 Elsevier Science Ltd.