(R)-3-(2-naphthyl)cyclohexanone | 608489-14-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-3-(2-naphthyl)cyclohexanone
• 英文别名: (3R)-3-naphthalen-2-ylcyclohexan-1-one
• CAS: 608489-14-1
• 化学式: C₁₆H₁₆O
• 分子量: 224.302
• InChiKey: CJZGZPTYKOPUPG-CQSZACIVSA-N

物化性质

• 沸点：
  396.0±31.0 °C(Predicted)
• 密度：
  1.114±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2-环己烯-1-酮 、 2,4,6-tris-(2-naphthyl)boroxine 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96%的产率得到(R)-3-(2-naphthyl)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

• Readily Accessible Chiral Diene Ligands for Rh-Catalyzed Enantioselective Conjugate Additions of Boronic Acids
  作者：Barry M. Trost、Aaron C. Burns、Thomas Tautz

  DOI：10.1021/ol201754c

  日期：2011.9.2

  the broad scope of the Pd-catalyzed asymmetric alkylation of meso- and d,l-divinylethylene carbonate, several chiral diene ligands were prepared in two steps from commercial materials. Subsequently, these ligands were evaluated in the Rh-catalyzed asymmetric conjugate addition of boronic acids to enones.

  由于Pd催化的内消旋和d，1-二乙烯基碳酸亚乙酯的不对称烷基化反应的广泛范围，从商业原料中分两步制备了几种手性二烯配体。随后，在硼酸到烯酮的Rh催化的不对称共轭加成中评估了这些配体。
• A Chiral Bis-Sulfoxide Ligand in Late-Transition Metal Catalysis; Rhodium-Catalyzed Asymmetric Addition of Arylboronic Acids to Electron-Deficient Olefins
  作者：Ronaldo Mariz、Xinjun Luan、Michele Gatti、Anthony Linden、Reto Dorta

  DOI：10.1021/ja710665q

  日期：2008.2.1

  A bis-sulfoxide with a binaphthyl backbone is introduced as a readily available, chiral ligand entity in late-transition metal catalysis. Ligand p-tol-BINASO [where p-tol-BINASO is 1,1‘-binaphthalene-2,2‘-diyl-bis-(p-tolylsulfoxide)] is obtained in pure form in one single synthetic step from relatively cheap, commercially available starting materials. Precatalyst [(P,R,R)-p-tol-BINASO}RhCl]2 was synthesized

  具有联萘骨架的双亚砜作为后过渡金属催化中容易获得的手性配体实体被引入。配体 p-tol-BINASO [其中 p-tol-BINASO 是 1,1'-联萘-2,2'-二基-双-(对甲苯基亚砜)] 在一个单一合成步骤中以纯形式从相对便宜的、市售原料。前催化剂 [(P,R,R)-p-tol-BINASO}RhCl]2 以高产率合成，并通过 X 射线衍射进行结构表征，并将结构数据与游离配体进行比较。该预催化剂在芳基硼酸与环状 α,β-不饱和酮和酯的不对称 1,4-加成反应中显示出优异的反应性和选择性。
• Chiral Sulfoxide-Olefin Ligands: Completely Switchable Stereoselectivity in Rhodium-Catalyzed Asymmetric Conjugate Additions
  作者：Guihua Chen、Jiangyang Gui、Liangchun Li、Jian Liao

  DOI：10.1002/anie.201102586

  日期：2011.8.8

  it both ways: A novel class of chiral sulfoxide‐olefin ligands was synthesized from a single chiral source. These ligands were evaluated in rhodium‐catalyzed 1,4‐additions of arylboronic acids to electron‐deficient olefins, and remarkable olefin‐directed reversal of stereoselectivity (up to >99 % ee, R isomer; 98 % ee, S isomer) was observed when the reversal ligand pair L1 (branched olefin) and L2

  两者兼有：从单一手性来源合成了一类新型的手性亚砜-烯烃配体。在铑催化的芳基硼酸的1,4加成反应中，对这些配体进行了评估，并观察到电子不足的烯烃，并 观察到烯烃定向的立体选择性显着逆转（高达99％ee，R 异构体； 98％ee，S异构体）。当使用反向配体对L1（支链烯烃）和L2（直链烯烃）时（参见方案）。
• Fine‐Tuning the Bicyclo[3.3.1]nona‐2,6‐diene Ligands: Second Generation 4,8‐Substituted Dienes for Rh‐Catalyzed Asymmetric 1,4‐Addition Reactions
  作者：Vidmantas Bieliūnas、Sigitas Stončius

  DOI：10.1002/cctc.202100638

  日期：2021.9.7

  C2-symmetric 4,8-endo,endo-bis(alkoxy) bicyclo[3.3.1]nona-2,6-diene ligands possessing additional 4,8-exo,exo substituents is reported. The 4,8-exo,exo groups provide a further element for fine-tuning of the ligand structure by enforcing conformational rigidity of the 4,8-endo,endo side chains. Such tetrasubstituted bicyclo[3.3.1]nona-2,6-dienes were employed as steering ligands in the rhodium-catalyzed arylation

  设计和合成了第二代C 2 -对称 4,8-内，内 -双（烷氧基）双环 [3.3.1] 壬 - 2,6-二烯配体，具有额外的 4,8-外，外取代基。4,8- exo,exo基团通过加强 4,8-内、内侧链的构象刚性为配体结构的微调提供了进一步的元素。这种四取代的双环[3.3.1]壬二烯-2,6-二烯在铑催化的环烯酮与芳基硼酸的芳基化反应中被用作导向配体，提供相应的1,4-加成产物，产率良好至极好（69- 99 %) 和高达 99 % ee 的对映选择性。
• Chiral Phosphorus-Olefin Ligands for the Rh^I-Catalyzed Asymmetric Addition of Aryl Boronic Acids to Electron-Deficient Olefins
  作者：Qian Chen、Liang Li、Guangli Zhou、Xiaoli Ma、Lu Zhang、Fang Guo、Yi Luo、Wujiong Xia

  DOI：10.1002/asia.201600143

  日期：2016.5.20

  New chiral phosphorus–olefin hybrid ligands derived from the rigid “privileged” l‐proline have been conveniently prepared and applied in the rhodium‐catalyzed asymmetric arylation of electron‐deficient olefins with arylboronic acids at room temperature; this reaction provides the desired products in excellent yields and high enantioselectivities. The origin of observed stereoselectivity has been investigated

  衍生自刚性“特权” 1-脯氨酸的新型手性磷-烯烃杂化配体已在室温下方便地制备并应用于铑催化的缺电子烯烃与芳基硼酸的不对称芳基化反应。该反应以优异的产率和高对映选择性提供了所需的产物。观察到的立体选择性的起源已通过密度泛函理论（DFT）计算进行了研究。