(R)-4-phenyl-4-(p-tolyl)butan-2-one | 1072832-14-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (R)-4-phenyl-4-(p-tolyl)butan-2-one
• 英文别名: (4R)-4-(4-methylphenyl)-4-phenylbutan-2-one
• CAS: 1072832-14-4
• 化学式: C₁₇H₁₈O
• 分子量: 238.329
• InChiKey: SWHBUSPOSRBPMB-QGZVFWFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 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：

  苯甲醛 在 chlorobis(ethylene)rhodium(I) dimer 、 C₂₇H₂₁O₂P 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 6.5h， 生成 (R)-4-phenyl-4-(p-tolyl)butan-2-one
  参考文献：
  名称：

  醛、甲基酮和芳基硼酸的顺序羟醛缩合-过渡金属催化的加成反应

  摘要：

  描述了醛与甲基酮的顺序羟醛缩合，然后是过渡金属催化的芳基硼酸加成反应以形成 β-取代的酮。通过使用基于 1,1'-spirobiindane-7,7'-二醇 (SPINOL) 的亚磷酸酯，还实现了此类顺序反应的不对称版本，ee 高达 92%。我们的研究提供了一种获得 β 取代酮的有效方法，并可能导致其他顺序/串联反应的发展，其中过渡金属催化的加成反应是关键步骤。

  DOI：

  10.1021/ol200457q

文献信息

• Electronically deficient ( Rax , S , S )-F 12 -C 3 -TunePhos and its applications in asymmetric 1,4-addition reactions
  作者：Shu-Bo Hu、Zhang-Pei Chen、Ji Zhou、Yong-Gui Zhou

  DOI：10.1016/j.tetlet.2016.03.072

  日期：2016.4

  diphosphine ligand (Rax,S,S)-F12-C3-TunePhos has been concisely synthesized. The electron-poor ligand features both chiral centers and chiral axis bearing fluoro-functional groups on each phosphorus phenyl ring based on C3-TunePhos backbone. The catalyst composed of this ligand and rhodium showed excellent activities and enantioselectivities in asymmetric 1,4-addition reactions of arylboronic acids to

  简明地合成了一种新型的电子缺陷的手性二膦配体（R ax，S，S）-F 12 -C 3 -TunePhos。贫电子配体的特征是基于C 3 -TunePhos主链的每个磷苯环上的手性中心和手性轴均带有氟官能团。由这种配体和铑组成的催化剂在芳基硼酸与ee高达99％的各种α，β-不饱和酮的不对称1,4-加成反应中显示出出色的活性和对映选择性。
• Chiral Tetrafluorobenzobarrelenes as Highly Efficient Ligands for the Rhodium-catalyzed Asymmetric 1,4-Addition of Arylboronic Acids
  作者：Takahiro Nishimura、Makoto Nagaosa、Tamio Hayashi

  DOI：10.1246/cl.2008.860

  日期：2008.8.5

  New C2-symmetric chiral diene ligands bearing a tetrafluorobenzobarrelene framework and (−)-menthyl groups as chiral auxiliaries were prepared through [4 + 2] cycloaddition of 1,4-bis((−)-menthoxym...

  通过 1,4-双((-)-薄荷醇的 [4 + 2] 环加成反应制备了带有四氟苯并茚骨架和 (-)-薄荷基作为手性助剂的新型 C2 对称手性二烯配体。
• A Diastereomeric Pair of Sulfoxide-containing Chiral MOP-type Ligands: Preparation and Application to Rhodium-catalyzed Asymmetric 1,4-Addition Reactions
  作者：Takashi Hoshi、Masataka Fujita、Shouta Matsushima、Hisahiro Hagiwara、Toshio Suzuki

  DOI：10.1246/cl.180260

  日期：2018.6.5

  pair of sulfoxide-containing chiral MOP-type ligands. These two ligands also represent the first monosulfoxide analogues of BINAP. The chiral ligand L2 was successfully applied to the highly enantioselective rhodium-catalyzed 1,4-addition between α,β-unsaturated ketones or esters and arylboronic acids, and exhibited a broad substrate scope when the reaction was performed using 1.5 mol% Rh in cyclohexane/H2O

  (R,SS)-亚砜-MOP (L2) 和 (R,RS)-亚砜-MOP (L3) 被开发为一对含亚砜的手性 MOP 型配体的非对映异构体。这两个配体也代表了 BINAP 的第一个单亚砜类似物。手性配体 L2 成功应用于高对映选择性铑催化的 α,β-不饱和酮或酯与芳基硼酸之间的 1,4-加成反应，并在使用 1.5 mol% Rh 的环己烷溶液进行反应时表现出广泛的底物范围/H2O (10:1) 在 40 °C 温和碱性条件下。
• Enantioselective Conjugate Addition of Stabilized Arylzinc Iodide to Enones: an Improved Protocol of the Hayashi Reaction
  作者：Gianluca Casotti、Vincenzo Rositano、Anna Iuliano

  DOI：10.1002/adsc.202001141

  日期：2021.2.16

  Stabilised arylzinc iodide, prepared by direct insertion of zinc into aryl iodides, were used as nucleophiles in the Hayashi Rh‐catalysed enantioselective conjugate addition to enones. The reaction conditions were optimized in the addition of phenylzinc iodide to 2‐cyclohexen‐1‐one, obtaining good yields and 99% ee of the addition product. The general applicability of the protocol was checked using

  通过将锌直接插入芳基碘化物中制备的稳定的芳基碘化碘化物被用作Hayashi Rh催化的烯酮对映体选择性共轭物的亲核试剂。优化了反应条件，将苯碘化锌添加到2-环己烯-1-酮中，获得了良好的收率和99％ee的加成产物。使用不同的芳基碘化碘和烯酮检查方案的一般适用性。具有卤素和亲电基团的有机金属试剂也已成功使用。
• Evaluation of Palladacycles as a Non-Rhodium Based Alternative for the Asymmetric Conjugate 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Enones
  作者：Jonathan Wong、Kennard Gan、Houguang Jeremy Chen、Sumod A. Pullarkat

  DOI：10.1002/adsc.201400473

  日期：2014.11.3

  AbstractThe asymmetric conjugate 1,4‐addition of arylboronic acids to α,β‐unsaturated carbonyl compounds is an extremely versatile and widely used organic transformation. While the rhodium(I)‐catalysed reaction has been thoroughly explored, the asymmetric palladium‐catalysed protocol is far less developed and understood, particularly with acyclic enones as substrates. Herein, we report the systematic evaluation of a series of metallacycles for this reaction and the conjugate addition of arylboronic acids to a wide range of α,β‐unsaturated enones, catalysed by an easily accessible and robust chiral phosphapalladacycle in high yields and enantioselectivities.magnified image