2-乙烯基-6,6-二甲基-5,7-二氧杂螺[2.5]辛烷-4,8-二酮 | 71107-18-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-乙烯基-6,6-二甲基-5,7-二氧杂螺[2.5]辛烷-4,8-二酮
• 英文名称: 6,6-dimethyl-1-vinyl-5,7-dioxaspiro[2.5]octane-4,8-dione
• 英文别名: 6,6-dimethyl-2-ethenyl-5,7-dioxaspiro[2.5]octane-4,8-dione；5,7-Dioxaspiro[2.5]octane-4,8-dione, 1-ethenyl-6,6-dimethyl-；2-ethenyl-6,6-dimethyl-5,7-dioxaspiro[2.5]octane-4,8-dione
• CAS: 71107-18-1
• 化学式: C₁₀H₁₂O₄
• 分子量: 196.203
• InChiKey: LHOWRYQIMFIXLH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-乙烯基-6,6-二甲基-5,7-二氧杂螺[2.5]辛烷-4,8-二酮 以83%的产率得到
  参考文献：
  名称：

  DANISHEFSKY S.; SINGH R. K., J. ORG. CHEM. , 1975, 40, NO 25, 3807-3808

  摘要：

  DOI：
• 作为产物：
  描述：

  丙二酸环(亚)异丙酯 、 顺式-1,2-二羟甲基乙烯 在 偶氮二甲酸二异丙酯 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以20%的产率得到2-乙烯基-6,6-二甲基-5,7-二氧杂螺[2.5]辛烷-4,8-二酮
  参考文献：
  名称：

  Mitsunobu C-Alkylation of Meldrum's Acids

  摘要：

  C-Dialkylation of Meldrum's acid (2a) and 5-benzyl Meldrum's acid (2b) can be achieved through Mitsunobu dehydration using allylic and arylmethyl alcohols as alkylating agents. This is the first time that the Mitsunobu reaction is successfully applied to the C-alkylation of a highly enolizable cyclic beta-dicarbonyl system. With primary (allylic and arylmethyl) alcohols, the alkylations always take place at the carbon bearing the hydroxy: group. For secondary allylic alcohols, a catalytic amount of Pd(0) must be added to enhance the regioselectivity of C-alkylation over O-alkylation. With (Ph(3)P)(4)Pd(0) as a catalyst, the reaction occurs specifically at the less hindered carbon, and the configuration of the resultant double bond is always trans. Attempts to monoalkylate Meldrum's acids 2a and 2b failed.

  DOI：

  10.1021/jo962288+

文献信息

• Disulfide-Bridged Peptides That Mediate Enantioselective Cycloadditions through Thiyl Radical Catalysis
  作者：Jonathan M. Ryss、Amanda K. Turek、Scott J. Miller

  DOI：10.1021/acs.orglett.8b00364

  日期：2018.3.16

  An enantioselective vinylcyclopropane ring-opening/cycloaddition cascade is described. The active thiyl radical catalysts are generated in situ via UV light-promoted homolysis of cystine-based dimers. Amide-functionalization of the peptide at the 4-proline position is essential for effective asymmetric induction. Stereochemical communication is dependent on steric interactions with this substituent

  描述了对映选择性的乙烯基环丙烷开环/环加成级联。通过基于胱氨酸的二聚体的紫外光促进的均质分解，活性硫基自由基催化剂被原位产生。肽在4-脯氨酸位置的酰胺功能化对于有效的不对称诱导至关重要。立体化学通讯取决于与该取代基的空间相互作用，该相互作用通过H键结合至肽主链而得以实现。
• Synergistic Catalysis: Enantioselective Ring Expansion of Vinyl Cyclopropanes Combining Four Catalytic Cycles for the Synthesis of Highly Substituted Spirocyclopentanes Bearing up to Four Stereocenters
  作者：Marta Meazza、Ramon Rios

  DOI：10.1002/chem.201601893

  日期：2016.7.11

  A double synergistic cascade reaction is reported, combining transition metal and amine catalysis. The reaction between vinyl cyclopropanes and enals renders the final cyclopentane derivatives in excellent yields and stereoselectivities.

  报道了双重协同级联反应，结合了过渡金属和胺催化。乙烯基环丙烷与烯醛之间的反应以极佳的收率和立体选择性提供了最终的环戊烷衍生物。
• Palladium-Catalyzed Diastereo- and Enantioselective Formal [3 + 2]-Cycloadditions of Substituted Vinylcyclopropanes
  作者：Barry M. Trost、Patrick J. Morris、Simon J. Sprague

  DOI：10.1021/ja309003x

  日期：2012.10.24

  We describe a palladium-catalyzed diastereo- and enantioselective formal [3 + 2]-cycloaddition between substituted vinylcyclopropanes and electron-deficient olefins in the form of azlactone- and Meldrum's acid alkylidenes to give highly substituted cyclopentane products. By modulation of the electronic properties of the vinylcyclopropane and the electron-deficient olefin, high levels of stereoselectivity

  我们描述了钯催化的非对映选择性和对映选择性形式的 [3 + 2]-环加成反应，在取代的乙烯基环丙烷和缺电子烯烃之间以 azlactone-和 Meldrum 的酸亚烷基的形式发生，得到高度取代的环戊烷产品。通过调节乙烯基环丙烷和缺电子烯烃的电子特性，获得了高水平的立体选择性。由催化剂提供的远程立体诱导，远离由配体产生的手性口袋，被认为是调用 Curtin-Hammett 原理的新机制的结果。
• Metal-Free Visible-Light-Promoted Trifluoromethylation of Vinylcyclopropanes Using Pyrylium Salt as a Photoredox Catalyst
  作者：Palasetty Chandu、Krishna Gopal Ghosh、Devarajulu Sureshkumar

  DOI：10.1021/acs.joc.9b01033

  日期：2019.7.5

  Visible-light-induced metal-free trifluoromethylation of activated, carbocyclic, and unactivated vinylcyclopropanes via a ring-opening reaction using the Langlois reagent (CF3SO2Na) is reported to synthesize allylic trifluoromethylated derivatives. Allylic trifluoromethylation was achieved by a photo-oxidative single electron transfer (SET) process at an ambient temperature and under metal-free conditions

  据报道，使用Langlois试剂（CF 3 SO 2 Na）通过开环反应，可见光诱导的活化，碳环和非活化乙烯基环丙烷的无金属三氟甲基化反应可合成烯丙基三氟甲基化衍生物。烯丙基三氟甲基化是通过在环境温度和无金属条件下通过光氧化单电子转移（SET）工艺以及使用吡喃鎓盐作为光氧化还原催化剂的可见光照射实现的。所报道的方法具有操作简单，基材范围广，官能团耐受性高和可扩展性的特点。
• Photoredox catalysed allylic trifluoromethylation via ring opening of vinyl cyclopropanes using Langlois reagent
  作者：Palasetty Chandu、Krishna Gopal Ghosh、Debabrata Das、Devarajulu Sureshkumar

  DOI：10.1016/j.tet.2019.130641

  日期：2019.11

  Trifluoromethylation of vinylcyclopropanes (VCPs) has been developed under mild reaction conditions to synthesize allylic trifluoromethylated derivatives with high yield and E/Z selectivity using visible light photo-redox catalysis and Langlois reagent (CF3SO2Na) as a trifluoromethylation source. Further, we demonstrate a gram scale synthesis procedure for a trifluoromethylation of vinylcyclopropane

  乙烯基环丙烷（VCP）的三氟甲基化已开发出来，可以在温和的反应条件下，使用可见光氧化还原催化和朗格洛斯试剂（CF 3 SO 2 Na）作为三氟甲基化源，以高收率和E / Z选择性合成烯丙基三氟甲基化衍生物。此外，我们证明了乙烯基环丙烷的三氟甲基化的克级合成程序。