1-(2-benzyloxy-3,6-dimethoxyphenyl)-1-triethylsiloxybut-3-en-2-one | 914604-17-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(2-benzyloxy-3,6-dimethoxyphenyl)-1-triethylsiloxybut-3-en-2-one
• 英文别名: 1-(3,6-Dimethoxy-2-phenylmethoxyphenyl)-1-triethylsilyloxybut-3-en-2-one
• CAS: 914604-17-4
• 化学式: C₂₅H₃₄O₅Si
• 分子量: 442.627
• InChiKey: YVQIDWOPQDBNQL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  31
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-(2-benzyloxy-3,6-dimethoxyphenyl)-1-triethylsiloxybut-3-en-2-one 在 palladium diacetate 、 palladium dihydroxide 盐酸 、 四丁基氯化铵 、 氢气 、 碳酸氢钠 、 环己烯 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 、 异丙醇 为溶剂， 反应 96.0h， 生成 trans-4,7-dimethoxy-3',4'-dihydro-3H-spiro[1-benzofuran-2,2'-chromen]-3-ol
  参考文献：
  名称：

  Synthesis of Bisbenzannulated SpiroketalsModel Studies for a Modular Approach to Rubromycins

  摘要：

  [GRAPHICS]A highly flexible synthesis of bisbenzannulated spiroketals is described with additions of lithiated methoxyallene to aryl aldehydes and Heck reactions as key steps. Subsequent hydrogenations and ketalizations afforded the desired spiroketals in good yields and with predominating trans-configuration. With model compound 30, already bearing the fully substituted naphthyl core of rubromycins, the ketalization proceeded efficiently providing the expected product 31 and the isopropoxy compound 32. Both products are advanced model compounds of heliquinomycin.

  DOI：

  10.1021/ol061932w
• 作为产物：
  描述：

  2-benzyloxy-3,6-dimethoxybenzaldehyde 在 正丁基锂 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 生成 1-(2-benzyloxy-3,6-dimethoxyphenyl)-1-triethylsiloxybut-3-en-2-one
  参考文献：
  名称：

  Synthesis of Bisbenzannulated SpiroketalsModel Studies for a Modular Approach to Rubromycins

  摘要：

  [GRAPHICS]A highly flexible synthesis of bisbenzannulated spiroketals is described with additions of lithiated methoxyallene to aryl aldehydes and Heck reactions as key steps. Subsequent hydrogenations and ketalizations afforded the desired spiroketals in good yields and with predominating trans-configuration. With model compound 30, already bearing the fully substituted naphthyl core of rubromycins, the ketalization proceeded efficiently providing the expected product 31 and the isopropoxy compound 32. Both products are advanced model compounds of heliquinomycin.

  DOI：

  10.1021/ol061932w

文献信息

• Model Studies for the Synthesis of Heliquinomycin: Preparation of New Spiroketals
  作者：Hans-Ulrich Reissig、Chelvam Venkatesh

  DOI：10.1055/s-0028-1083194

  日期：2008.11

  New model compounds were investigated within our efforts to synthesize the natural product heliquinomycin. We could provide good evidence that electronic effects prevent the spiroketal formation of compounds such as 5 incorporating an isocoumarin moiety. As a consequence, precursors 16 and 26 were prepared, which do not exert the strong electron-withdrawing effect of the methoxycarbonyl group present in 5. Dihydroisocumarin derivative 10 and phthalide 25 were coupled by Heck reactions with enone 4 to provide the required precursors 16 and 26. After reductive debenzylation the resulting intermediates were treated with anhydrous hydrochloric acid in alcohols to give spiroketals 18-20 and 28, 29 in reasonable yields. The spiroketalizations occur under thermodynamic control affording products with the hydroxyl group in a trans-relationship with respect to the pyran oxygen atom. Attempts to oxidatively convert dihydroisocumarin 19 into an isocoumarin derivative failed. In one attempt a ring contraction to new spiroketal 24 was observed.

  在合成天然产品氦喹霉素的过程中，我们研究了新的模型化合物。我们可以提供确凿证据，证明电子效应阻止了含有异香豆素分子的化合物（如 5）形成螺酮。因此，我们制备了前体 16 和 26，它们不会像 5 中的甲氧基羰基那样产生强烈的夺电子效应。二氢异香豆素衍生物 10 和邻苯二甲酸盐 25 与烯酮 4 发生赫克反应，得到所需的前体 16 和 26。还原脱苄基化后，生成的中间体在醇中用无水盐酸处理，得到螺酮 18-20 和 28、29，收率合理。螺酮化反应是在热力学控制下进行的，生成物中的羟基与吡喃氧原子呈反式关系。将二氢异鼠李素 19 氧化转化为异香豆素衍生物的尝试失败了。在一次尝试中，观察到环收缩成新的螺酮 24。
• Synthesis of Bisbenzannulated SpiroketalsModel Studies for a Modular Approach to Rubromycins
  作者：Sebastian Sörgel、Cengiz Azap、Hans-Ulrich Reissig

  DOI：10.1021/ol061932w

  日期：2006.10.1

  [GRAPHICS]A highly flexible synthesis of bisbenzannulated spiroketals is described with additions of lithiated methoxyallene to aryl aldehydes and Heck reactions as key steps. Subsequent hydrogenations and ketalizations afforded the desired spiroketals in good yields and with predominating trans-configuration. With model compound 30, already bearing the fully substituted naphthyl core of rubromycins, the ketalization proceeded efficiently providing the expected product 31 and the isopropoxy compound 32. Both products are advanced model compounds of heliquinomycin.