(1R,4S,5R,6S)-5,6-bis(((tert-butyldimethylsilyl)oxy)methyl)bicyclo[2.2.1]hept-2-ene

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1R,4S,5R,6S)-5,6-bis(((tert-butyldimethylsilyl)oxy)methyl)bicyclo[2.2.1]hept-2-ene
• 英文别名: tert-butyl-[[(1S,2R,3S,4R)-3-[[tert-butyl(dimethyl)silyl]oxymethyl]-2-bicyclo[2.2.1]hept-5-enyl]methoxy]-dimethylsilane
• 化学式: C₂₁H₄₂O₂Si₂
• 分子量: 382.734
• InChiKey: SQCYHCCJSARFHG-QGFMHUBQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.47
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 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：

  (1R,4S,5R,6S)-5,6-bis(((tert-butyldimethylsilyl)oxy)methyl)bicyclo[2.2.1]hept-2-ene 、 烯丙基三甲基硅烷 在 钌 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以99%的产率得到
  参考文献：
  名称：

  A New Highly Efficient Ruthenium Metathesis Catalyst This work was supported by the Fonds der Chemischen Industrie.

  摘要：

  DOI：

  10.1002/1521-3773(20020703)41:13<2403::aid-anie2403>3.0.co;2-f

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）。
• Optically Pure <i>C</i>₁-Symmetric Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Asymmetric Olefin Metathesis
  作者：Jennifer Morvan、François Vermersch、Ziyun Zhang、Laura Falivene、Thomas Vives、Vincent Dorcet、Thierry Roisnel、Christophe Crévisy、Luigi Cavallo、Nicolas Vanthuyne、Guy Bertrand、Rodolphe Jazzar、Marc Mauduit

  DOI：10.1021/jacs.0c10705

  日期：2020.11.25

  An expedient access to the first optically pure ruthenium complexes containing C1-symmetric cyclic (alkyl)(amino)carbene ligands is reported. They demonstrate excellent catalytic performances in asymmetric olefin metathesis with high enantioselectivities (up to 92% ee). Preliminary mechanistic insights provided by density functional theory models highlight the origin of the enantioselectivity.

  报道了获得第一个包含 C1 对称环状（烷基）（氨基）卡宾配体的光学纯钌配合物的便利途径。它们在不对称烯烃复分解反应中表现出优异的催化性能，具有高对映选择性（高达 92% ee）。密度泛函理论模型提供的初步机械见解突出了对映选择性的起源。
• Chiral Ru-Based Complexes for Asymmetric Olefin Metathesis:  Enhancement of Catalyst Activity through Steric and Electronic Modifications
  作者：Joshua J. Van Veldhuizen、Dennis G. Gillingham、Steven B. Garber、Osamu Kataoka、Amir H. Hoveyda

  DOI：10.1021/ja0302228

  日期：2003.10.1

  Design, synthesis, characterization, and catalytic activity of six enantiomerically pure Ru-based metathesis catalysts are disclosed (3a-3f). The new chiral catalysts were prepared through steric and electronic alterations of the parent catalyst system (3). The present studies indicate that the effect of structural modifications of chiral complex 3 does not always correspond to those of the related achiral complexes. The present findings illustrate that modified Ru complexes (3e and 3f) deliver reactivity levels that are more than 2 orders of magnitude higher than 3. Reactivity and physical data are provided that shed light on the origin of activity differences. Some members of the new generation of chiral Ru catalysts promote asymmetric ring-opening (AROM) and ring-closing (ARCM) metatheses that cannot be effected by the first generation chiral catalyst (3).
• Selective Ring-Opening Olefin Metathesis of Functionalized Monosubstituted Olefins
  作者：Matthias F. Schneider、Norbert Lucas、Janna Velder、Siegfried Blechert

  DOI：10.1002/anie.199702571

  日期：1997.2.14
• Highly Selective Ring-Opening/Cross-Metathesis Reactions of Norbornene Derivatives Using Selenocarbene Complexes as Catalysts
  作者：Hiroyuki Katayama、Hideto Urushima、Tsuneo Nishioka、Chikaya Wada、Masato Nagao、Fumiyuki Ozawa

  DOI：10.1002/1521-3773(20001215)39:24<4513::aid-anie4513>3.0.co;2-c

  日期：2000.12.15