(S)-2-(2-bromo-5-methoxyphenyl)-4-isopropyl-4,5-dihydrooxazole | 1400638-89-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (S)-2-(2-bromo-5-methoxyphenyl)-4-isopropyl-4,5-dihydrooxazole
• 英文别名: (4S)-4,5-dihydro-2-(5′-methoxy-2′-bromophenyl)-4-isopropyloxazole
• CAS: 1400638-89-2
• 化学式: C₁₃H₁₆BrNO₂
• 分子量: 298.18
• InChiKey: DVHIQFWUJJAAKF-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.26
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  30.82
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (S)-2-(2-bromo-5-methoxyphenyl)-4-isopropyl-4,5-dihydrooxazole 、 (1R,2S,5R)-(-)-menthyl (S)-p-toluenesulfinate 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以44%的产率得到(S)-4-isopropyl-2-(5-methoxy-2-((S)-p-tolylsulfinyl)phenyl)-4,5-dihydrooxazole
  参考文献：
  名称：

  Theoretical Elucidation of Potential Enantioselectivity in a Pd-Catalyzed Aromatic C–H Coupling Reaction

  摘要：

  The mechanism of an aromatic C-H coupling reaction between heteroarenes and arylboronic acids using a Pd catalyst was theoretically and experimentally investigated. We identified the C-B transmetalation as the rate determining step. The (S)-catalyst-reactant complex was found to be stabilized by hyperconjugation between pi-orbitals on the tolyl group and the S-O sigma* antibonding orbital in the catalyst ligand. Our findings suggest routes for the design of new, improved Pd catalysts with higher stereoselectivity.

  DOI：

  10.1021/acs.joc.6b02675
• 作为产物：
  描述：

  2-溴-5-甲氧基苯甲酸 在 1-羟基苯并三唑 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 三乙胺 、 对甲苯磺酰氯 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 生成 (S)-2-(2-bromo-5-methoxyphenyl)-4-isopropyl-4,5-dihydrooxazole
  参考文献：
  名称：

  Theoretical Elucidation of Potential Enantioselectivity in a Pd-Catalyzed Aromatic C–H Coupling Reaction

  摘要：

  The mechanism of an aromatic C-H coupling reaction between heteroarenes and arylboronic acids using a Pd catalyst was theoretically and experimentally investigated. We identified the C-B transmetalation as the rate determining step. The (S)-catalyst-reactant complex was found to be stabilized by hyperconjugation between pi-orbitals on the tolyl group and the S-O sigma* antibonding orbital in the catalyst ligand. Our findings suggest routes for the design of new, improved Pd catalysts with higher stereoselectivity.

  DOI：

  10.1021/acs.joc.6b02675

文献信息

• Investigation of the Electronic Origin of Asymmetric Induction in Palladium-Catalyzed Allylic Substitutions with Phosphinooxazoline (PHOX) Ligands by Hammett and Swain–Lupton Analysis of the ¹³C NMR Chemical Shifts of the (π-Allyl)palladium Intermediates
  作者：Paul B. Armstrong、Elizabeth A. Dembicer、Andrew J. DesBois、Jay T. Fitzgerald、Janet K. Gehrmann、Nathaniel C. Nelson、Amelia L. Noble、Richard C. Bunt

  DOI：10.1021/om3007163

  日期：2012.10.8

  typically obtained with PHOX ligands exceeds the approximately 8/1 ratio of exo to endo intermediates. Swain–Lupton analysis reveals the importance of both resonance and field effects by the substituents regardless of their location and supports the overall electronic control model for enantioselection by PHOX ligands. For rational chiral ligand design and electronic tuning of ligand properties, these results

  同构的4'-和5'-取代的膦基恶唑啉（PHOX）配体用于探测对（1,3-二苯基烯丙基）钯PHOX配体络合物的对映选择性亲核加成的电子来源。Hammett分析烯丙基C-1和C-3碳的13 C NMR化学位移表明，主要的外型非对映异构体较不易受C-1和C-3处的差异变化的影响，并且取代基的位置较小对这些变化的影响。相反，次要的内非对映异构体更容易受到差异13的影响在C-1和C-3处的C NMR变化以及取代基的位置对这些变化影响更大。内非对映异构体通过横跨钯中心的氮和磷原子的连接显示出显着的“顺式作用”，这解释了其较低的反应性，因此，通常用PHOX配体获得的对映选择性如何超过外切与内切中间体的约8/1比例。Swain-Lupton分析揭示了无论取代基的位置如何，共振和场效应的重要性，并支持了PHOX配体对映异构的整体电子控制模型。为了进行合理的手性配体设计和电子调节配体性质，