(4R,4’R)-2,2’-ethylidenebis[4,5-dihydro-4-phenyloxazole] | 644994-50-3

• 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: (4R,4’R)-2,2’-ethylidenebis[4,5-dihydro-4-phenyloxazole]
• 英文别名: 2,2-bis((R)-4-phenyl-4,5-dihydrooxazol-2-yl)ethane；1,1-bis[(4R)-4-phenyloxazolin-2-yl]ethane；(4R,4'R)-2,2'-(Ethane-1,1-diyl)bis(4-phenyl-4,5-dihydrooxazole)；(4R)-4-phenyl-2-[1-[(4R)-4-phenyl-4,5-dihydro-1,3-oxazol-2-yl]ethyl]-4,5-dihydro-1,3-oxazole
• CAS: 644994-50-3
• 化学式: C₂₀H₂₀N₂O₂
• 分子量: 320.391
• InChiKey: AQHCGFJCLPHENX-ROUUACIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4R,4’R)-2,2’-ethylidenebis[4,5-dihydro-4-phenyloxazole] 在 sodium hydroxide 、 正丁基锂 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.5h， 生成 11,11-Bis-((R)-4-phenyl-4,5-dihydro-oxazol-2-yl)-dodecane-1-thiol
  参考文献：
  名称：

  Reusable nano-sized chiral bisoxazoline catalysts

  摘要：

  The nano-sized gold particle-based chiral catalyst having two kinds of alkyl thiol spacers, one of which is substituted with the chiral bisoxazoline/copper(II) complex at the end, behaves as reusable homogeneous catalyst. This gold particle complex acts as nearly homogeneous catalyst in the ene reaction between 2-phenylpropene and ethyl glyoxylate in dichloromethane, while it undergoes dense aggregation when diluted with hexane so as to be separated by simple filtration. Thus, the catalyst can be recovered after the completion of reaction by the repeated sequences of solvent exchange, centrifugal treatment, and decantation, followed by the recharge of substrates, and the situation is ready for the second reaction. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.08.100
• 作为产物：
  描述：

  在 4-二甲氨基吡啶 、 三乙胺 、 对甲苯磺酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以68%的产率得到(4R,4’R)-2,2’-ethylidenebis[4,5-dihydro-4-phenyloxazole]
  参考文献：
  名称：

  固定在氟反相硅胶上的全氟化双（二氢恶唑）配合物，作为对映选择性Diels的可回收催化剂？der木反应

  摘要：

  这三种不同的全氟烷基-标记的双（二氢恶唑）铜络合物19 - 21合成，并通过氟氟上反相硅胶（FRPSG）非共价地固定化氟相互作用（方案2和3）。这些负载的催化剂被成功地应用到不对称狄尔斯阿尔德H中反应2 O和CH中2氯2（方案4）。除了亲二烯体的高转化率外，我们观察到对映体过量在H 2 O中高达88％，在CH 2 Cl 2中高达97％。，我们能够多次回收和再利用这些催化系统。尽管催化剂的负载量相对较高，但铜的浸出量却非常低，仅为2.4至5.9 ppm。

  DOI：

  10.1002/hlca.201200380

文献信息

• Using a Tripod as a Chiral Chelating Ligand: Chemical Exchange Between Equivalent Molecular Structures in Palladium Catalysis with 1,1,1-Tris(oxazolinyl)ethane (“Trisox”)
  作者：Carole Foltz、Markus Enders、Stéphane Bellemin-Laponnaz、Hubert Wadepohl、Lutz H. Gade

  DOI：10.1002/chem.200700307

  日期：2007.7.16

  (BOX=bis(oxazolinyl)dimethylmethane) ligands with [Pd(nbd)(alkene)] (nbd=norbornadiene, alkene=maleic anhydride or tetracyanoethylene). X-ray diffraction studies of the iPr-trisox and Ph-trisox complexes (3a and 3b) established Y-shaped trigonal planar coordination geometries with the trisox ligand coordinated in a bidentate fashion, whilst the pi-coordinated maleic anhydride ligand adopts one of the two possible

  对于仅用作二齿配体的情况，三重对称手性Podands可以简化关键催化中间体的立体化学。这适用于这样的系统，其中在不同的kappa2配位形式之间进行化学交换，并且其中非配位侧臂可能在催化循环的某个较早或较晚阶段起直接或间接的作用。钯（II）催化的烯丙基取代沿这些方向提供了适当的测试反应。一系列中性二氯钯（II）配合物[PdCl2（iPr-trisox）]（1a），[PdCl2（Ph-trisox）]（1b），[PdCl2（Bn-trisox）]（1c）和[PdCl2（Ind） -三（trisox）]（1d）（三（trisox = 1,1,1-三（恶唑啉基）乙烷）]是通过将相应的三（trisox）衍生物与[PdCl2（PhCN）2]反应合成的，并通过15N NMR光谱进行了表征。借助于在600 MHz NMR光谱仪上的低温冷却NMR探针，可以实现不具有同位素富集和“正常”样品浓度的杂核的直接检测。配位恶唑啉环的15N核在delta
• Bisoxazolines with one and two sidearms: stereodirecting ligands for copper-catalysed asymmetric allylic oxidations of alkenes
  作者：Markus Seitz、Carmine Capacchione、Stéphane Bellemin-Laponnaz、Hubert Wadepohl、Benjamin D. Ward、Lutz H. Gade

  DOI：10.1039/b512570g

  日期：——

  A series of sidearm functionalized bisoxazoline ligands has been synthesized by reaction of the monolithiated methylbis(oxazolinyl)}methane with the appropriate electrophiles, and tested in the copper catalyzed asymmetric allylic oxidation of cyclohexene (“Kharasch–Sosnovski” reaction). The observed enantioselectivities were higher (up to 85% ee) than for the unfunctionalized bisoxazoline (“BOX”) derivatives (ca. 60% ee). Regardless of the functional groups incorporated into the sidearm unit, the ee's obtained for the different derivatives were essentially indistinguishable. This implies that the sidearms do not interfere directly in this reaction and only play an indirect role by virtue of their steric demand. Three of the copper complexes have been characterized by X-ray diffraction, establishing a distorted octahedral coordination geometry around the copper atom in all three cases. In the elongated distorted CuN2O4 octahedra, the two nitrogen atoms of the oxazolines and one oxygen atom of each acetate ligand occupy the ‘equatorial’ positions whereas the sidearms do not interact with the metal centres.

  通过单锂化甲基双（恶唑啉基）}甲烷与适当的亲电物反应，合成了一系列侧耳官能化双恶唑啉配体，并在铜催化的环己烯不对称烯丙基氧化（"Kharasch-Sosnovski "反应）中进行了测试。与未官能化的双噁唑啉（"BOX"）衍生物（约 60% ee）相比，观察到的对映体选择性更高（高达 85% ee）。无论在侧耳单元中加入何种官能团，不同衍生物的ee基本上没有区别。这意味着，侧基不会直接干扰该反应，而只是通过其立体需求发挥间接作用。通过 X 射线衍射对其中三种铜配合物进行了表征，在所有三种情况下都确定了铜原子周围的扭曲八面体配位几何。在拉长变形的 CuN2O4 八面体中，恶唑啉的两个氮原子和每个醋酸配体的一个氧原子占据 "赤道 "位置，而侧翼则与金属中心没有相互作用。
• Highly Recyclable Self-Supported Chiral Catalysts for the Enantioselective α-Hydrazination of β-Ketoesters
  作者：Maria Torres、Aline Maisse-François、Stéphane Bellemin-Laponnaz

  DOI：10.1002/cctc.201300395

  日期：2013.10

  Multitopic chiral copper complexes based on bis(oxazoline) have been applied in the enantioselective α‐hydrazination of β‐ketoesters. High yields and excellent enantioselectivities were obtained. Furthermore, the catalytic systems have been recovered in up to ten cycles without loss of activity or enantioselectivity. The formation of coordination polymers [polytopic ligand–Cu]n has been confirmed by UV/Vis

  基于双（恶唑啉）的多主题手性铜配合物已用于β-酮酸酯的对映选择性α-酰化。获得了高产率和优异的对映选择性。此外，催化体系已在多达十个循环中被回收，而没有损失活性或对映选择性。UV / Vis滴定法已经证实了配位聚合物[多位配体-Cu] n的形成。在增加配体的局部性时观察到明显的金属浸出。通过非线性效应实验研究了催化剂的性质。
• Modular Synthesis of Chiral Homo- and Heterotrisoxazolines. Improving the Enantioselectivity in the Asymmetric Michael Addition of Indole to Benzylidene Malonate
  作者：Meng-Chun Ye、Bin Li、Jian Zhou、Xiu-Li Sun、Yong Tang

  DOI：10.1021/jo050595m

  日期：2005.7.1

  A simple approach to a diverse set of chiral trisoxazolines is described. Deprotonation of bisoxazolines 2, followed by treatment of 2-chloromethyloxazolines 3, affords chiral trisoxazolines, including chiral homo- and hetero-trisoxazolines in good to high yields. These trisoxazolines are successfully applied in the asymmetric reaction of indole with benzylidene malonate, and ee's up to 93% were obtained.
• Soluble polyisobutylene-supported reusable catalysts for olefin cyclopropanation
  作者：David E. Bergbreiter、Jianhua Tian

  DOI：10.1016/j.tetlet.2007.04.147

  日期：2007.6

  Polyisobutylene oligomers (PIB) have been used as soluble supports for the immobilization of cyclopropanation catalysts. In addition to simple carboxylate ligands, chiral bisoxazolines have been successfully attached to these heptane-soluble polymers. Their use and recovery has been investigated using cyclopropanation of styrene as an example. An achiral PIB-bound Rh(II) catalyst showed good activity and could be easily recycled nine times using a liquid-liquid biphasic separation technique. PIB-supported bisoxazoline ligands for Cu(I) catalysts were also prepared. These chiral catalysts showed good catalytic activity and stereoselectivity. A chiral ligand prepared from phenylglycine provided the most effective stereocontrol and gave the trans- and cis-cyclopropanation products in 94% ee and 68% ee, respectively. All three PIB-bound chiral bisoxazoline-Cu(I) catalysts prepared could be reused five to six times. (c) 2007 Elsevier Ltd. All rights reserved.