(1R*,4S*,7S*)-1,3,3-trimethoxy-7-ethanoyl-5-methoxycarbonylbicyclo<2.2.2>oct-5-en-2-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R*,4S*,7S*)-1,3,3-trimethoxy-7-ethanoyl-5-methoxycarbonylbicyclo<2.2.2>oct-5-en-2-one
• 英文别名: 1,3,3-trimethoxy-7-ethanoyl-5-methoxycarbonylbicyclo[2.2.2]oct-5-en-2-one；methyl (1R,4S,8R)-8-acetyl-4,6,6-trimethoxy-5-oxobicyclo[2.2.2]oct-2-ene-2-carboxylate
• 化学式: C₁₅H₂₀O₇
• 分子量: 312.32
• InChiKey: YEDXRFCSZJCKIN-WDMOLILDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  三氟甲磺酸三甲基硅酯 、 (1R*,4S*,7S*)-1,3,3-trimethoxy-7-ethanoyl-5-methoxycarbonylbicyclo<2.2.2>oct-5-en-2-one 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以89%的产率得到methyl (1RS,4SR,8SR)-8-(1-trimethylsilyloxyvinyl)-4,6,6-trimethoxy-5-oxobicyclo[2.2.2]oct-2-ene-2-carboxylate
  参考文献：
  名称：

  从2-甲氧基苯酚的立体控制合成多官能化顺式十氢萘：（±）-Eremopetasidione，（±）-3β-Angylyloxyfuranoeremophilane和（±）-3β-Methacryloyloxyfuranoeremophilane的总合成

  摘要：

  描述了多官能化顺式十氢化萘的四步立体控制合成，涉及2-甲氧基苯酚的氧化，分子间Diels-Alder反应，烯化和Cope重排。这种有效策略的应用是通过共同的中间体21从甲酚和乙基乙烯基酮中完成对（±）-erpetpetasidione，（±）-3β-angelyloxyfuranoeremophilane和（±）-3β-甲基丙烯酰氧基呋喃戊二酮的总合成的。

  DOI：

  10.1021/jo702115x
• 作为产物：
  描述：

  甲醇 、 丁香酸甲酯 、 丁烯酮 在 碘苯 、 间氯过氧苯甲酸 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以85%的产率得到(1R*,4S*,7S*)-1,3,3-trimethoxy-7-ethanoyl-5-methoxycarbonylbicyclo<2.2.2>oct-5-en-2-one
  参考文献：
  名称：

  碘苯和间氯过苯甲酸介导的苯酚氧化脱芳烃

  摘要：

  通过原位生成PhIO 2（一种高价碘（V）物质），可以通过催化量的碘苯将2-和4-取代的苯酚氧化脱芳香化为其相应的苯醌单缩酮，并将m -CPBA作为助氧化剂。瞬态生成的邻苯二酚单缩酮进一步与各种亲二烯体进行Diels-Alder反应，以高选择性和高收率提供密集取代的双环[2.2.2]辛烯酮。这种方法的特点是易于使用的试剂，成本效益，安全性，简便性，选择性，多样性和优异的收率。

  DOI：

  10.1016/j.tetlet.2016.07.078

文献信息

• Generation, Stability, Dimerization, and Diels−Alder Reactions of Masked <i>o</i>-Benzoquinones. Synthesis of Substituted Bicyclo[2.2.2]octenones from 2-Methoxyphenols
  作者：Chun-Chen Liao、Chrong-Shyua Chu、Tsung-Ho Lee、Polisetti Dharma Rao、San Ko、Ling-Duan Song、Huey-Chin Shiao

  DOI：10.1021/jo9901891

  日期：1999.5.1

  Diels-Alder reactions of labile and readily dimerizing masked o-benzoquinones, i.e., substituted 6,6-dimethoxy-2,4-cyclohexadienones with electron-deficient dienophiles that resulted in the development of an efficient and reliable one-pot method for the preparation of highly functionalized bicyclo[2.2.2]octenones, are described. Oxidation of 2-methoxyphenols 8, 9, 11, 13, and 14 with (diacetoxy)iodobenzene in methanol afforded the corresponding masked o-benzoquinones 1, 2, 4, 6, and 7, which are not stable enough to be isolated and are found to dimerize under reaction conditions in a highly regio- and stereoselective manner to provide the Diels-Alder dimers 22, 23, 25, 27, and 28 respectively. On the other hand, masked o-benzoquinones 3 and 5, derived from phenols 10 and 12, respectively, were found to be quite labile and provided a complex mixture of products. However, masked o-benzoquinones 1-7, when generated in the presence of dienophiles such as methyl acrylate, methyl methacrylate, and methyl vinyl ketone, underwent highly regio- and stereoselective intermolecular Diels-Alder reactions to furnish variously substituted bicyclo[2.2.2]octenones 15-21(a-c). While the Diels-Alder reactions of masked o-benzoquinone 5 were found to be low-yielding, masked o-benzoquinones 1-4, 6, and 7 provided the desired adducts in good to high yields. Attempts are made to explain the observed regio- and stereoselectivity of these Diels-Alder reactions in terms of frontier molecular orbital theory.
• Iodobenzene and m-chloroperbenzoic acid mediated oxidative dearomatization of phenols
  作者：Neha Taneja、Rama Krishna Peddinti

  DOI：10.1016/j.tetlet.2016.07.078

  日期：2016.8

  iodobenzene, and m-CPBA as a co-oxidant has been achieved via in situ generation of PhIO2, a hypervalent iodine(V) species. The transiently generated orthobenzoquinone monoketals further underwent Diels–Alder reaction with various dienophiles to furnish densely substituted bicyclo[2.2.2]octenones in high selectivities and yields. This methodology features ready availability of reagents, cost effectiveness, safety

  通过原位生成PhIO 2（一种高价碘（V）物质），可以通过催化量的碘苯将2-和4-取代的苯酚氧化脱芳香化为其相应的苯醌单缩酮，并将m -CPBA作为助氧化剂。瞬态生成的邻苯二酚单缩酮进一步与各种亲二烯体进行Diels-Alder反应，以高选择性和高收率提供密集取代的双环[2.2.2]辛烯酮。这种方法的特点是易于使用的试剂，成本效益，安全性，简便性，选择性，多样性和优异的收率。
• Stereocontrolled Synthesis of Polyfunctionalized <i>cis</i>-Decalins from 2-Methoxyphenols:  Total Syntheses of (±)-Eremopetasidione, (±)-3β-Angeloyloxyfuranoeremophilane, and (±)-3β-Methacryloyloxyfuranoeremophilane
  作者：Day-Shin Hsu、Po-Yi Hsu、Yen-Chun Lee、Chun-Chen Liao

  DOI：10.1021/jo702115x

  日期：2008.4.1

  A four-step stereocontrolled synthesis of polyfunctionalized cis-decalins is described, involving oxidation of 2-methoxyphenol, intermolecular Diels−Alder reaction, olefination, and Cope rearrangement. Application of this efficient strategy to the total syntheses of (±)-eremopetasidione, (±)-3β-angeloyloxyfuranoeremophilane, and (±)-3β-methacryloyloxyfuranoeremophilane was accomplished from creosol

  描述了多官能化顺式十氢化萘的四步立体控制合成，涉及2-甲氧基苯酚的氧化，分子间Diels-Alder反应，烯化和Cope重排。这种有效策略的应用是通过共同的中间体21从甲酚和乙基乙烯基酮中完成对（±）-erpetpetasidione，（±）-3β-angelyloxyfuranoeremophilane和（±）-3β-甲基丙烯酰氧基呋喃戊二酮的总合成的。