(S)-3-(4-bromophenyl)-1-phenylpentan-1-one

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: (S)-3-(4-bromophenyl)-1-phenylpentan-1-one
• 英文别名: (3S)-1-phenyl-3-(4-bromophenyl)-pentanone；3-(4-bromophenyl)-1-phenylpentan-1-one；1-phenyl-3-(4-bromophenyl)pentanone；(3S)-3-(4-bromophenyl)-1-phenylpentan-1-one
• 化学式: C₁₇H₁₇BrO
• 分子量: 317.225
• InChiKey: JPUPHOOXCFRPQX-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  19
• 可旋转键数：
  5
• 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：

  4-溴查尔酮 、 diethylzinc 在 bis(acetylacetonate)nickel(II) 、 (1S,2R,4R)-7,7-dimethyl-1-morpholin-4-yl-bicyclo[2.2.1]heptan-2-ol 、 盐酸 作用下， 以 丙腈 、 水 为溶剂， 反应 30.25h， 以76%的产率得到(S)-3-(4-bromophenyl)-1-phenylpentan-1-one
  参考文献：
  名称：

  Enantioselective conjugate addition of dialkylzincs to α,β-unsaturated enones catalyzed by Ni(acac)2 and (+)-(1S,2R)-7,7-dimethyl-1-morpholinoisonorborneol

  摘要：

  A mixture of chiral ligand 4 [(+)-MINBOL] and Ni(acac)(2) (12.5 and 0.5 mol % respectively) is able to successfully catalyze the enantioselective conjugate 1,4-addition of dialkylzinc to alpha,beta-unsaturated enones in propionitrile to give the corresponding chiral Michael adducts in good yields and with high enantioselectivities (up to 93% ee). (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.01.010

文献信息

• The effects of solvent on switchable stereoselectivity: copper-catalyzed asymmetric conjugate additions using D2-symmetric biphenyl phosphoramidite ligands
  作者：Han Yu、Fang Xie、Zhenni Ma、Yangang Liu、Wanbin Zhang

  DOI：10.1039/c2ob25730k

  日期：——

  A highly enantioselective copper-catalyzed conjugate addition of diethylzinc to acyclic aromatic enones was developed with phosphoramidite ligands bearing a D2-symmetric biphenyl backbone. This type of reaction demonstrated that toluene and THF solvents can completely reverse the absolute configuration of the products, thus simplifying the process of accessing either enantiomer (S: 92% ee, 94% yield;

  铜的高对映选择性铜催化共轭加成 二乙基锌用带有D 2对称联苯主链的亚磷酰胺配体开发了无环芳族烯酮。这种反应表明甲苯THF溶剂可以完全逆转产物的绝对构型，从而简化了获得任一种对映异构体的过程（S：92％ee，94％收率；R：99％ee，96％收率）。
• Switchable Stereoselectivity: The Effects of Substituents on the D2-Symmetric Biphenyl Backbone of Phosphoramidites in Copper-Catalyzed Asymmetric Conjugate Addition Reactions with Triethylaluminium
  作者：Han Yu、Fang Xie、Zhenni Ma、Yangang Liu、Wanbin Zhang

  DOI：10.1002/adsc.201101007

  日期：2012.7.9

  A highly enantioselective copper‐catalyzed conjugate addition with triethylaluminium was developed using phosphoramidite ligands bearing a D2‐symmetric biphenyl backbone. For these ligands we demonstrated that the 3,3′,5,5′‐substituents on the biphenyl backbone can completely reverse the absolute configuration of the products.

  使用带有D 2对称联苯骨架的亚磷酰胺配体，开发了具有三乙基铝的高对映选择性的铜催化共轭加成物。对于这些配体，我们证明了联苯主链上的3,3'，5,5'-取代基可以完全逆转产物的绝对构型。
• Copper-catalyzed enantioselective 1,4-conjugate addition of dialkylzinc reagents to α,β- and α,β,γ,δ-unsaturated ketones
  作者：Rukeya Rexiti、Jian Lu、Feng Sha、Xin-Yan Wu

  DOI：10.1016/j.tet.2019.05.029

  日期：2019.6

  An enantioselective Cu(II)-catalyzed conjugate addition of dialkylzinc reagents to α,β- or α,β,γ,δ-unsaturated ketones with chiral cyclohexane-based amidophosphine ligands was developed. With 2 mol% of Cu(OAc)2·H2O/L5, the conjugate addition of diethylzinc to α,β-unsaturated ketones was achieved in good-to-excellent yields (up to 98%) and high enantioselectivities (up to 92% ee). This catalytic system

  开发了一种手性环己烷基酰胺基膦配体的对映选择性Cu（II）催化二烷基锌试剂共轭加成到α，β-或α，β，γ，δ-不饱和酮上的方法。使用2 mol％的Cu（OAc）2 ·H 2 O / L5，可以将二乙基锌共轭添加到α，β-不饱和酮中，收率良好至优异（最高98％），对映选择性高（最高90％）。 92％ee）。该催化体系显示对于将Et 2 Zn 1，（4 - E）加成到（2 E，4 E）-1,5-二苯基戊-2,4-dien-1-one上是有效的，产率为85％，90 ％ee。另外，Cu（OTf）2 / L11为1摩尔％，α，β，γ，δ-不饱和酮的共轭加成反应具有1,4-区域选择性，良好的收率（79-86％）和出色的对映选择性（高达97％ee）。
• Regulation of the flexibility of planar chiral [2.2]paracyclophane ligands and its significant impact on enantioselectivity in asymmetric reactions of diethylzinc with carbonyl compounds
  作者：Xun-Wei Wu、Tang-Zhi Zhang、Ke Yuan、Xue-Long Hou

  DOI：10.1016/j.tetasy.2004.06.026

  日期：2004.8

  A series of planar chiral ligands derived from [2.2]paracyclophane were synthesized and applied as catalysts in enantioselective additions of diethylzinc to aldehydes and α,β-unsaturated ketones. When ligand 10 with a dimethyl hydroxymethyl as the substituent was used, the enantioselectivity of the reaction of diethylzinc with aldehydes was much higher than when using ligand 3c with diphenyl hydroxymethyl

  合成了一系列衍生自[2.2]对环环烷的平面手性配体，并将其用作催化剂，将二乙基锌与醛和α，β-不饱和酮进行对映选择性加成。当使用具有二甲基羟甲基作为取代基的配体10时，二乙基锌与醛的反应的对映选择性比使用具有二苯基羟甲基作为取代基的配体3c的对映选择性高得多。当使用羟甲基取代的配体7b时，将二乙基锌1,4-加成到α，β-不饱和酮上时，情况相同，ee为63-83％，而如果使用配体3c，则几乎不提供对映选择性。还研究了平面手性的作用。
• METHOD OF ENANTIOSELECTIVE ADDITION TO ENONES
  申请人：UANG Biing-Jiun

  公开号：US20110282101A1

  公开（公告）日：2011-11-17

  The present invention relates to a method of enantioselective addition to enones, including: reacting R 3 (CH 2 ) p CH═CR 5 C(═O)Y(CH 2 ) q R 4 with R 6 ZnR 7 in the presence of a compound represented by the following formula (I) and a transition metal catalyst, in which Y, p, q, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are defined the same as the specification. Accordingly, the present invention can perform asymmetric conjugate addition in high yields and enantioselectivity.

  本发明涉及一种对烯酮进行对映选择性加成的方法，包括：在存在以下式（I）所代表的化合物和过渡金属催化剂的情况下，将R3(CH2)pCH═CR5C(═O)Y(CH2)qR4与R6ZnR7反应，其中Y、p、q、R1、R2、R3、R4、R5、R6和R7的定义与规范相同。因此，本发明可以在高产率和对映选择性下进行不对称共轭加成。