spiro<4,5>dec-7-ene-1,4-dione | 151700-27-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: spiro<4,5>dec-7-ene-1,4-dione
• 英文别名: spiro[4.5]dec-8-ene-1,4-dione
• CAS: 151700-27-5
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: PKXXDSZVBHGQJN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.64
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  spiro<4,5>dec-7-ene-1,4-dione 生成 (1S,5S)-1-hydroxyspiro[4.5]dec-8-en-4-one
  参考文献：
  名称：

  Liu Pei-Ying, Burnell D. Jean, J. Chem. Soc. Chem. Commun, (1994) N 10, S 1183-1184

  摘要：

  DOI：
• 作为产物：
  描述：

  二(三甲基硅氧基)环丁烯 、 1,4-dioxaspiro<4,5>dec-7-ene 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以75%的产率得到spiro<4,5>dec-7-ene-1,4-dione
  参考文献：
  名称：

  Formation of 2,2-disubstituted 1,3-cyclopentanediones from ketals with 1,2-bis(trimethylsilyloxy)cyclobutene

  摘要：

  通过路易斯酸催化的反应，使用1,2-双(三甲基硅氧基)环丁烯与没有受阻碍的缩酮，直接形成2,2-二取代的1,3-环戊二酮化合物，产率良好至优秀，但立体位阻显著降低了产率。位于缩酮α或β位置的羰基，或者与缩酮α位置相邻的碳-碳双键会完全停止反应。正酯不会以合成有用的产率产生双酰化产物。

  DOI：

  10.1139/v93-169

文献信息

• Selective formation of angular tricyclic compounds by ruthenium-mediated ring-rearrangement metathesis
  作者：Fuye Gao、Craig T. M. Stamp、Paul D. Thornton、T. Stanley Cameron、Lauren E. Doyle、David O. Miller、D. Jean Burnell

  DOI：10.1039/c1cc15452d

  日期：——

  Unsaturated spirocyclic substrates bearing two alkenyl chains underwent ruthenium-mediated ring-rearrangement metathesis through relaying cyclohexene and cycloheptene moieties to give angularly fused tricyclics. In some instances where two products were expected, high degrees of selectivity were observed. In one instance the structural parameter leading to selectivity was very subtle; in others the transformation favoured the formation of products with a cis-fused cyclohexene moiety. An unusual transformation involving ring-opening, double-bond migration, and then ring-closing was observed.

  具有两个烯丙基链的不饱和螺环底物通过钌介导的环重排交叉反应，借助环己烯和环庚烯的中继形成了角度结合的三环化合物。在某些情况下，预期产物有两个，但观察到高选择性。在一种情况下，导致选择性的结构参数非常微妙；而在其他情况下，转化更倾向于形成具有顺式连接的环己烯部分的产物。观察到一种不寻常的转化过程，涉及开环、双键迁移，然后再闭环。
• Facial selectivity in nucleophilic reactions of spirocyclic ketones can be controlled by a distant, orthogonal double bond
  作者：Pei-Ying Liu、D. Jean Burnell

  DOI：10.1039/c39940001183

  日期：——

  Spiro[4.5]dec-7-ene-1,4-dione and derivatives substituted at C-7, C-8, and/or C-9 gave products of reaction with methyllithium and with sodium borohydride that in every instance favoured nucleophilic carbonyl attack on the face syn to the double bond; the results are consistent with stereoelectronic control, and the selectivity correlates with a difference in the abilities of the orthogonal C–C bond to donate electron density.

  在C-7、C-8和/或C-9上被取代的螺[4.5]癸-7-烯-1,4-二酮及其衍生物与甲基锂和硼氢化钠反应，在每种情况下都倾向于对双键的同侧进行亲核羰基攻击；结果与立体电子控制一致，选择性与正交C-C键的供电子密度能力差异相关。
• Lewis Acid Catalyzed Geminal Acylation Reaction of Ketones with 1,2-Bis[(trimethylsilyl)oxy]cyclobutene: Direct Formation of 2,2-Disubstituted 1,3-Cyclopentanediones
  作者：Tracy J. Jenkins、D. Jean Burnell

  DOI：10.1021/jo00085a041

  日期：1994.3

  Ketones reacted with 1,2-bis((trimethylsilyl)oxy)cyclobutene (1) under catalysis by boron trifluoride etherate to yield 2,2-disubstituted 1,3-cyclopentanedione products via silylated cyclobutanone intermediates in a two-step, one-pot process. In many instances addition of a small amount of water to the reaction medium after completion of the first step assisted the subsequent rearrangement to the product, such that reversion of the intermediate to the starting ketone became an insignificant process. Yields were best with cyclohexanones (>90%), but steric hindrance and conjugated double bonds reduced yields considerably.
• Liu Pei-Ying, Burnell D. Jean, J. Chem. Soc. Chem. Commun, (1994) N 10, S 1183-1184
  作者：Liu Pei-Ying, Burnell D. Jean

  DOI：——

  日期：——
• Formation of 2,2-disubstituted 1,3-cyclopentanediones from ketals with 1,2-bis(trimethylsilyloxy)cyclobutene
  作者：Yong-Jin Wu、Dean W. Strickland、Tracy J. Jenkins、Pei-Ying Liu、D. Jean Burnell

  DOI：10.1139/v93-169

  日期：1993.9.1

  The direct formation of 2,2-disubstituted 1,3-cyclopentanedione compounds by a Lewis acid catalysed reaction with 1,2-bis(trimethylsilyloxy)cyclobutene proceeds in good to excellent yields with unhindered ketals, but steric hindrance reduces the yields considerably. A carbonyl group α or β to the ketal, or a carbon–carbon double bond α to the ketal, stops the reaction completely. Orthoesters do not give geminally acylated products in synthetically useful yields.

  通过路易斯酸催化的反应，使用1,2-双(三甲基硅氧基)环丁烯与没有受阻碍的缩酮，直接形成2,2-二取代的1,3-环戊二酮化合物，产率良好至优秀，但立体位阻显著降低了产率。位于缩酮α或β位置的羰基，或者与缩酮α位置相邻的碳-碳双键会完全停止反应。正酯不会以合成有用的产率产生双酰化产物。