6-tert-butyldimethylsilyloxynaphthalene-1,4-dione | 691390-69-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 6-tert-butyldimethylsilyloxynaphthalene-1,4-dione
• 英文别名: 6-(dimethyl-t-butylsilyloxy)-1,4-naphthoquinone；6-[Tert-butyl(dimethyl)silyl]oxynaphthalene-1,4-dione
• CAS: 691390-69-9
• 化学式: C₁₆H₂₀O₃Si
• 分子量: 288.418
• InChiKey: HXKORMAVHXOOJO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.01
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(triisopropylsiloxy)-1,3-butadiene 、 6-tert-butyldimethylsilyloxynaphthalene-1,4-dione 在 oxazaborolidinium⁽¹⁺⁾*Tf₂N^(1-) 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以95%的产率得到(4aR,9aS)-2-(triisopropylsilyl)oxy-1,4,4a,9a-tetrahydro-7-t-butyldimethylsilylanthracene-9,10-dione
  参考文献：
  名称：

  Enantioselective and Structure-Selective Diels−Alder Reactions of Unsymmetrical Quinones Catalyzed by a Chiral Oxazaborolidinium Cation. Predictive Selection Rules

  摘要：

  The chiral oxazaborolidinium cation 1 promotes Diels-Alder reactions between 2-triisopropylsilyloxy-1,3-butadiene and a number of unsymmetrical 1,4-benzoquinones in a highly enantioselective and structurally selective manner. The basis for the enantioselectivity is explained rationally in terms of a preferred type of transition-state assembly. Selection rules have been developed that allow the prediction of the principal reaction product of Diels-Alder reaction between unsymmetrical diene and quinone components.

  DOI：

  10.1021/ja049323b
• 作为产物：
  描述：

  1,6-二羟基萘 在 咪唑 、 salcomine 、 氧气 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 10.33h， 生成 6-tert-butyldimethylsilyloxynaphthalene-1,4-dione
  参考文献：
  名称：

  Enantioselective and Structure-Selective Diels−Alder Reactions of Unsymmetrical Quinones Catalyzed by a Chiral Oxazaborolidinium Cation. Predictive Selection Rules

  摘要：

  The chiral oxazaborolidinium cation 1 promotes Diels-Alder reactions between 2-triisopropylsilyloxy-1,3-butadiene and a number of unsymmetrical 1,4-benzoquinones in a highly enantioselective and structurally selective manner. The basis for the enantioselectivity is explained rationally in terms of a preferred type of transition-state assembly. Selection rules have been developed that allow the prediction of the principal reaction product of Diels-Alder reaction between unsymmetrical diene and quinone components.

  DOI：

  10.1021/ja049323b

文献信息

• Generation of Endocyclic Vinyl Carbene Complexes via Gold-Catalyzed Oxidative Cyclization of Terminal Diynes: Toward Naphthoquinones and Carbazolequinones
  作者：Chao Shu、Chong-Yang Shi、Qing Sun、Bo Zhou、Tian-You Li、Qiao He、Xin Lu、Rai-Shung Liu、Long-Wu Ye

  DOI：10.1021/acscatal.8b04455

  日期：2019.2.1

  generation of endocyclic vinyl carbene complexes was involved in this oxidative cyclization, which is distinctively different from previous protocols. This method allows the facile synthesis of various valuable naphthoquinones and carbazolequinones from readily available diynes under exceptionally mild reaction conditions and features a broad substrate scope and wide functional group tolerance. Moreover

  在过去的几十年中，涉及卡宾/炔烃复分解的卡宾级联反应引起了人们的极大关注，因为这种化学方法具有巨大的潜力来构建复杂的环状分子。然而，在这些反应中形成的乙烯基金属类胡萝卜素仅限于环外碳烯，并且内环乙烯基卡宾配合物的产生仍未探索。在这里，我们报告了前所未有的金催化末端二炔的氧化环化反应。重要的是，这种氧化环化过程涉及内环乙烯基卡宾配合物的产生，这与以前的方案截然不同。该方法可以在非常温和的反应条件下轻松地从容易获得的二炔中轻松合成各种有价值的萘醌和咔唑醌，并且具有广泛的底物范围和宽泛的官能团耐受性。而且，理论计算为该环化反应的不同选择性提供了进一步的证据。