(2R)-2-but-2-en-2-yl-3-methyl-2,5-dihydrofuran

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: (2R)-2-but-2-en-2-yl-3-methyl-2,5-dihydrofuran
• 化学式: C₉H₁₄O
• 分子量: 138.21
• InChiKey: XKUWZBDIOAZASA-SECBINFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  3,5-Dimethyl-4-prop-2-enoxyhepta-2,5-diene 在 [(4S,5S)-1,3-bis(2-isopropylphenyl)-4,5-dimethylimidazolin-2-ylidene]dichloro(benzylidene)(tricyclohexylphosphine)ruthenium(II) 、 sodium iodide 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以99%的产率得到(2R)-2-but-2-en-2-yl-3-methyl-2,5-dihydrofuran
  参考文献：
  名称：

  对称性在钌催化的烯烃封闭环复分解中的关键作用

  摘要：

  进行了带有N-杂环卡宾（NHC）配体的Ru基预催化剂的合成，该配体在NHC主链上带有顺式和反式甲基和具有不同空间体积的芳基N-取代基。所述monophospine孺预催化剂的催化行为（图7a，图7b，8，和图8b）中的溶液相比，游离膦的催化剂的相应的家庭（9，9b的，10和10b中的环- ）烯烃的封闭复分解（RCM）。这些催化剂显示出高的效率在RCM反应和顺-异构体7和9一尤其被证明是通过RCM形成四取代烯烃时活性最高的催化剂之一。进行受阻烯烃的整个RCM催化循环DFT研究，理顺催化剂的不同行为，顺式和反对NHC骨干甲基组。理论结果不仅揭示了NHC对称性如何影响催化剂的整体活性，而且还给出了有关烯烃RCM关键步骤的相关且更为笼统的指示。

  DOI：

  10.1002/chem.201100483

文献信息

• Highly Active Chiral Ruthenium-Based Metathesis Catalysts through a Monosubstitution in the N-Heterocyclic Carbene
  作者：Sascha Tiede、Anke Berger、David Schlesiger、Daniel Rost、Anja Lühl、Siegfried Blechert

  DOI：10.1002/anie.201000940

  日期：2010.5.25

  Single (substitution) is better: New chiral ruthenium metathesis (pre)catalysts with a monosubstituted carbon atom in the N‐heterocyclic carbene ligand are highly stable in solution, initiate easily, show very high enantioselectivity and excellent E selectivity in asymmetric ring‐opening cross‐metathesis (see scheme).

  单（取代）更好：N-杂环卡宾配体中具有单取代碳原子的新型手性钌复分解（预）催化剂在溶液中高度稳定，易于引发，在非对称开环交叉中显示出很高的对映选择性和极好的E选择性复分解（请参阅方案）。
• Amino acids as chiral anionic ligands for ruthenium based asymmetric olefin metathesis
  作者：Elisa Ivry、Amos Ben-Asuly、Israel Goldberg、N. Gabriel Lemcoff

  DOI：10.1039/c5cc00052a

  日期：——

  Several amino acid ligands were introduced into the Hoveyda-Grubbs 2nd generation complex by a facile anionic ligand exchange. The chiral pre-catalysts obtained displayed enantioselectivity in asymmetric ring-closing and ring-opening cross-metathesis reactions. Reduction of the lability of the carboxylate ligands was found to be cardinal for improving the observed enantiomeric product enrichment.

  通过简便的阴离子配体交换，将几种氨基酸配体引入到Hoveyda-Grubbs第二代复合物中。获得的手性预催化剂在不对称的闭环和开环交叉复分解反应中显示出对映选择性。发现减少羧酸酯配体的不稳定性是改善所观察到的对映体产物富集的主要方法。
• Helicenes as Chirality-Inducing Groups in Transition-Metal Catalysis: The First Helically Chiral Olefin Metathesis Catalyst
  作者：Manfred Karras、Michał Dąbrowski、Radek Pohl、Jiří Rybáček、Jaroslav Vacek、Lucie Bednárová、Karol Grela、Ivo Starý、Irena G. Stará、Bernd Schmidt

  DOI：10.1002/chem.201802786

  日期：2018.8.1

  Kinetic data were acquired for benchmark test reactions and compared to an achiral catalyst. The helically chiral Ru‐catalyst was evaluated in asymmetric ring‐closing metathesis (RCM) and ring‐opening metathesis–cross‐metathesis (ROM/CM) reactions, which proceeded with promising levels of enantioselectivity. Extensive NMR‐spectroscopic investigations and a DFT geometry optimization were performed

  在过渡金属催化的转化中，螺旋手性是一种新颖的对映选择性诱导性质。本文以不对称烯烃复分解为例说明了该原理。这项工作报告了由氨基hel烯衍生的咪唑鎓盐合成的第一个螺旋手性Ru‐NHC亚烷基络合物，并与第一代Hoveyda-Grubbs催化剂连接。获得了基准测试反应的动力学数据，并将其与非手性催化剂进行了比较。在不对称的闭环复分解（RCM）和开环复分解-交叉复分解（ROM / CM）反应中评估了螺旋手性Ru催化剂，这些反应的对映选择性水平很高。进行了广泛的NMR光谱研究和DFT几何优化。
• Novel Olefin Metathesis Ruthenium Catalysts Bearing Backbone-Substituted Unsymmetrical NHC Ligands
  作者：Veronica Paradiso、Valerio Bertolasi、Fabia Grisi

  DOI：10.1021/om500731k

  日期：2014.11.10

  Ru-based catalysts containing unsymmetrical N-heterocyclic carbene (NHC) ligands with phenyl substituents on the backbone in syn and anti stereochemical relationships have been easily prepared and fully characterized. Preliminary investigation revealed that, depending on the backbone configuration, the new Ru complexes displayed different catalytic behaviors in representative olefin metathesis reactions

  容易制备并充分表征了稳定的Ru基催化剂，该催化剂含有不对称的N-杂环卡宾（NHC）配体，在主链上具有顺式和反立体化学关系的苯基取代基。初步研究表明，取决于骨架构型，新的钌配合物在代表性的烯烃复分解反应中显示出不同的催化行为。
• Asymmetric ring-closing metathesis reactions involving achiral and meso substrates
  申请人：Massachusetts Institute of Technology

  公开号：US06346652B1

  公开（公告）日：2002-02-12

  A composition and method for the catalytic conversion of a racemic mixture of dienes to a cyclic olefin by a ring-closing metathesis (RCM) reaction are disclosed. The composition, a transition metal complex with an M═C reaction site, contains a bidentate dialkoxide of at least 80% optical purity. Because the M═C reaction site is of a sufficient shape specificity, conferred in part by the dialkoxide of sufficient rigidity and a M═N—R1 site, reacting the composition with a mixture of two enantiomeric dienes results in an olefin metathesis product that has at least a 50% enantiomeric excess of one enantiomer in the mixture. A method is also provided for reacting a composition with a racemic diene mixture to generate a metathesis product that has an enantiomeric excess of at least 50%. Methods are also provided for catalytic enantioselective desymmetrization. One method involves an olefin metathesis reaction with a molecular substrate having a plane of symmetry to form a product free of a plane of symmetry. Another method provides a desymmetrization reaction to occur in the absence of solvent. A method for producing quaternary carbon centers through a desymmetrization reaction is also described.

  揭示了一种用于催化将二烯的外消旋混合物转化为环烯烃的组合物和方法，通过环闭合茂合反应（RCM）。该组合物是一个过渡金属配合物，具有一个M═C反应位点，含有至少80%光学纯度的双醚基。由于M═C反应位点具有足够的形状特异性，部分由足够刚度的双醚基和M═N—R1位点赋予，将该组合物与两个对映异构的二烯混合物反应会产生至少一个对映异构体的烯烃茂合物产物，其在混合物中具有至少50%的对映异构体过量。还提供了一种方法，用于将组合物与外消旋二烯混合物反应，生成具有至少50%对映异构体过量的茂合物产物。还提供了用于催化对映选择性非对称去对称化的方法。一种方法涉及与具有对称面的分子底物进行烯烃茂合反应，形成无对称面的产物。另一种方法提供了在无溶剂存在的情况下进行去对称化反应的方法。还描述了通过去对称化反应产生季碳中心的方法。