(R,R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene | 608489-13-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: (R,R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene
• 英文别名: (1R,4R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene；(R,R)-Bn-nbd*
• CAS: 608489-13-0
• 化学式: C₂₁H₂₀
• 分子量: 272.39
• InChiKey: NMAAYCBIZZGVPA-SFTDATJTSA-N

物化性质

• 沸点：
  414.7±40.0 °C(Predicted)
• 密度：
  1.114±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  chlorobis(ethylene)rhodium(I) dimer 、 (R,R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene 以 氘代氯仿 为溶剂， 生成 [RhCl((1R,4R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene)]2
  参考文献：
  名称：

  A Chiral Chelating Diene as a New Type of Chiral Ligand for Transition Metal Catalysts:  Its Preparation and Use for the Rhodium-Catalyzed Asymmetric 1,4-Addition

  摘要：

  As a new type of chiral ligand, a C2-symmetric norbornadiene derivative (1R,4R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene (1) was prepared and used for the rhodium-catalyzed asymmetric addition of organoboron and -tin reagents to alpha,beta-unsaturated ketones, which gave high yields of the 1,4-addition products with up to 99% enantioselectivity.

  DOI：

  10.1021/ja037367z
• 作为产物：
  描述：

  (,)-双环[2.2.1]庚烷-2,5-二酮 在 盐酸 、 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 正丁基锂 、 对甲苯磺酸 、 二异丙胺 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 1.0h， 生成 (R,R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene
  参考文献：
  名称：

  A Chiral Chelating Diene as a New Type of Chiral Ligand for Transition Metal Catalysts:  Its Preparation and Use for the Rhodium-Catalyzed Asymmetric 1,4-Addition

  摘要：

  As a new type of chiral ligand, a C2-symmetric norbornadiene derivative (1R,4R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene (1) was prepared and used for the rhodium-catalyzed asymmetric addition of organoboron and -tin reagents to alpha,beta-unsaturated ketones, which gave high yields of the 1,4-addition products with up to 99% enantioselectivity.

  DOI：

  10.1021/ja037367z
• 作为试剂：
  描述：

  2-环己烯-1-酮 、 4-氟苯硼酸酐 在 氢氧化钾 、 bis(ethylene)rhodium(I) chloride dimer 、 (R,R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene 作用下， 以 1,4-二氧六环 为溶剂， 反应 1.0h， 以91%的产率得到(R)-3-(4-fluorophenyl)cyclohexanone
  参考文献：
  名称：

  A Chiral Chelating Diene as a New Type of Chiral Ligand for Transition Metal Catalysts:  Its Preparation and Use for the Rhodium-Catalyzed Asymmetric 1,4-Addition

  摘要：

  As a new type of chiral ligand, a C2-symmetric norbornadiene derivative (1R,4R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene (1) was prepared and used for the rhodium-catalyzed asymmetric addition of organoboron and -tin reagents to alpha,beta-unsaturated ketones, which gave high yields of the 1,4-addition products with up to 99% enantioselectivity.

  DOI：

  10.1021/ja037367z

文献信息

• Expanding the <i>C</i>₂-Symmetric Bicyclo[2.2.1]hepta-2,5-diene Ligand Family:  Concise Synthesis and Catalytic Activity in Rhodium-Catalyzed Asymmetric Addition
  作者：Guillaume Berthon-Gelloz、Tamio Hayashi

  DOI：10.1021/jo061385s

  日期：2006.11.1

  achieved through the formation of the corresponding stable [RhCl(diene)]2 complexes. These chiral rhodium complexes displayed high activity and enantioselectivity (up to 99% ee) in the rhodium-catalyzed 1,4-addition and 1,2-addition of phenylboronic acid to cyclic enones and N-sulfonylimines, respectively.

  从容易获得的双环[2.2.1]开始，通过两步顺序制备对映体纯的新的C 2对称双环[2.2.1]庚-2,5-二烯，在2和5位带有甲基和苯基取代基。庚2,5-二酮。由于这些二烯的不稳定性或挥发性，它们的分离是通过形成相应的稳定的[RhCl（diene）] 2复合物来实现的。这些手性铑配合物分别在铑催化的苯基硼酸向环烯酮和N-磺酰亚胺类化合物的1,4-加成和1,2-加成中显示出高活性和对映选择性（高达99％ee）。
• Chiral Supramolecular U-Shaped Catalysts Induce the Multiselective Diels–Alder Reaction of Propargyl Aldehyde
  作者：Manabu Hatano、Tatsuhiro Sakamoto、Tomokazu Mizuno、Yuta Goto、Kazuaki Ishihara

  DOI：10.1021/jacs.8b09974

  日期：2018.11.28

  The Diels-Alder reaction, which is a traditional [4 + 2] cycloaddition with two carbon-carbon bond formations, is one of the most powerful tools to synthesize versatile and unique six-membered rings. We show that chiral supramolecular U-shaped boron Lewis acid catalysts promote the unprecedented multiselective Diels-Alder reaction of propargyl aldehyde with cyclic dienes. Independent from the substrate

  Diels-Alder 反应是一种传统的 [4 + 2] 环加成反应，具有两个碳-碳键形成，是合成通用且独特的六元环的最强大工具之一。我们表明手性超分子 U 形硼路易斯酸催化剂促进了炔丙醛与环二烯前所未有的多选择性 Diels-Alder 反应。独立于底物控制，对映-、内/外-、π-面-、区域-、位点和底物选择性可以通过本 U 形催化剂进行控制。所得反应产物可用于手性二烯配体和(+)-沙霉素关键中间体的简明合成。这里介绍的结果可能部分有助于开发用于多选择性反应的人工酶样超分子催化剂，
• A Chiral Chelating Diene as a New Type of Chiral Ligand for Transition Metal Catalysts:  Its Preparation and Use for the Rhodium-Catalyzed Asymmetric 1,4-Addition
  作者：Tamio Hayashi、Kazuhito Ueyama、Norihito Tokunaga、Kazuhiro Yoshida

  DOI：10.1021/ja037367z

  日期：2003.9.1

  As a new type of chiral ligand, a C2-symmetric norbornadiene derivative (1R,4R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene (1) was prepared and used for the rhodium-catalyzed asymmetric addition of organoboron and -tin reagents to alpha,beta-unsaturated ketones, which gave high yields of the 1,4-addition products with up to 99% enantioselectivity.