5,5-di-but-2-ynyl-2,2-dimethyl-[1,3]dioxane

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,5-di-but-2-ynyl-2,2-dimethyl-[1,3]dioxane
• 英文别名: 5,5-di(but-2-yn-1-yl)-2,2-dimethyl-1,3-dioxane；5,5-Bis(but-2-ynyl)-2,2-dimethyl-1,3-dioxane
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: JNOCWHLGVMHZOB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  二氧化碳 、 5,5-di-but-2-ynyl-2,2-dimethyl-[1,3]dioxane 在 bis(1,5-cyclooctadiene)nickel (0) 1,3-双(2,6-二异丙基苯基)咪唑-2-烯 作用下， 以 甲苯 为溶剂， 60.0 ℃ 、101.33 kPa 条件下， 反应 2.0h， 以98%的产率得到11,11-dimethyl-10,12-dioxa-spiro[4,5]decyl-3,6-dimethyl-pyran-2-one
  参考文献：
  名称：

  Efficient Nickel-Catalyzed [2 + 2 + 2] Cycloaddition of CO₂ and Diynes

  摘要：

  A mild and general route for preparing 2-pyrones from CO2 and diynes is described. Under only 1 atm of CO2, excellent yields of pyrone are obtained using catalytic amounts of Ni(COD)2 and imidazolylidene ligand, IPr. In addition, stoichiometric reactions between the isolated complex Ni(IPr)2, diynes, and CO2 suggest that the pathway involves initial reaction with CO2 as the key step.

  DOI：

  10.1021/ja027438e

文献信息

• Atroposelective [2+2+2] cycloadditions catalyzed by a rhodium(i)–chiral phosphate system
  作者：Mylène Augé、Marion Barbazanges、Anh Tuan Tran、Antoine Simonneau、Paulin Elley、Hani Amouri、Corinne Aubert、Louis Fensterbank、Vincent Gandon、Max Malacria、Jamal Moussa、Cyril Ollivier

  DOI：10.1039/c3cc43188f

  日期：——

  cationic Rh(I)-catalyzed [2+2+2] cycloaddition reactions between diynes and isocyanates relying on the chiral anion strategy have been devised. In the presence of [Rh(cod)Cl]2, 1,4-bis(diphenylphosphino)butane, and the silver phosphate salt Ag(S)-TRIP as the unique source of chirality, axially chiral pyridones were isolated with ees up to 82%. This approach is novel in the field of chiral anion-mediated

  依靠手性阴离子策略，设计了二炔与异氰酸酯之间的对映选择性阳离子Rh（I）催化的[2 + 2 + 2]环加成反应。在[Rh（cod）Cl] 2、1,4-双（二苯基膦基）丁烷和磷酸银盐Ag（S）-TRIP作为唯一手性来源的情况下，分离出轴向手性吡啶酮，直到82％。该方法在手性阴离子介导的不对称催化领域中是新颖的，因为迄今为止对映选择性的转化仍然是空前的。它也被证明是对基于手性L型配体的经典策略的补充。
• Rhodium-Catalyzed Decarboxylative Cycloaddition Route to Substituted Anilines
  作者：Kainan Zhang、Janis Louie

  DOI：10.1021/jo200236h

  日期：2011.6.3

  A convenient method for preparing substituted anilines via a Rh-catalyzed [2 + 2 + 2] cycloaddition reaction of diynes and 2-oxazolone was discovered. The initial cycloaddition adducts undergo facile decarboxylation of carbon dioxide to afford aniline products. Reaction conditions are mild, and only 3 mol % Rh catalyst is required. High regioselectivity was observed when an unsymmetrical diyne was used as a starting material.
• Double-Stereodifferentiation in Rhodium-Catalyzed [2 + 2 + 2] Cycloaddition: Chiral Ligand/Chiral Counterion Matched Pair
  作者：Mylène Augé、Alexandra Feraldi-Xypolia、Marion Barbazanges、Corinne Aubert、Louis Fensterbank、Vincent Gandon、Emilie Kolodziej、Cyril Ollivier

  DOI：10.1021/acs.orglett.5b01738

  日期：2015.8.7

  The first enantioselective metal-catalyzed [2 + 2 + 2] cycloaddition involving a double asymmetric induction has been devised. It relies on the use of an in situ generated chiral cationic rhodium(I) catalyst with a matched chiral ligand/chiral counterion pair. Careful optimization of the catalytic system, as well as of the reaction conditions, led to atroposelective [2 + 2 + 2] pyridone cycloadducts with high ees up to 96%. This strategy outperformed those previously described involving a chiral ligand only or a chiral counterion only.
• Efficient Nickel-Catalyzed [2 + 2 + 2] Cycloaddition of CO₂ and Diynes
  作者：Janis Louie、John E. Gibby、Marc V. Farnworth、Thomas N. Tekavec

  DOI：10.1021/ja027438e

  日期：2002.12.1

  A mild and general route for preparing 2-pyrones from CO2 and diynes is described. Under only 1 atm of CO2, excellent yields of pyrone are obtained using catalytic amounts of Ni(COD)2 and imidazolylidene ligand, IPr. In addition, stoichiometric reactions between the isolated complex Ni(IPr)2, diynes, and CO2 suggest that the pathway involves initial reaction with CO2 as the key step.