2-(3-溴苯基)-2-甲基环氧乙烷 | 73761-78-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-(3-溴苯基)-2-甲基环氧乙烷
• 英文名称: 2-(3-bromophenyl)-2-methyloxirane
• 英文别名: 2-methyl-2-(3-bromophenyl)oxirane；Oxirane, 2-(3-bromophenyl)-2-methyl-
• CAS: 73761-78-1
• 化学式: C₉H₉BrO
• 分子量: 213.074
• InChiKey: YAFAYOIACQUPKC-UHFFFAOYSA-N

物化性质

• 沸点：
  259.2±28.0 °C(Predicted)
• 密度：
  1.489±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(3-溴苯基)-2-甲基环氧乙烷 在 C₃₆H₅₄IrNP⁽¹⁺⁾*C₃₂H₁₂BF₂₄^(1-) 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以97%的产率得到2-(3-bromophenyl)propanal
  参考文献：
  名称：

  An air-stable cationic iridium hydride as a highly active and general catalyst for the isomerization of terminal epoxides

  摘要：

  我们描述了使用一种空气稳定的铱氢化物催化剂将末端环氧化物异构化为具有完美区域选择性的醛的方法。

  DOI：

  10.1039/c4cc05260a
• 作为产物：
  描述：

  1-溴-3-(丙-1-烯-2-基)苯 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以81%的产率得到2-(3-溴苯基)-2-甲基环氧乙烷
  参考文献：
  名称：

  Isomerization of Terminal Epoxides by a [Pd–H] Catalyst: A Combined Experimental and Theoretical Mechanistic Study

  摘要：

  An unusual palladium hydride complex has been shown to be a competent catalyst in the isomerization of a variety of terminal and internal epoxides. The reaction displayed broad scope and synthetic utility. Experimental and theoretical evidence are provided for an unprecedented hydride mechanism characterized by two distinct enantio-determining steps. These results hold promise for the development of an enantioselective variant of the reaction.

  DOI：

  10.1021/ja400325w

文献信息

• Complementary Catalytic Strategies to Access ?-Chiral Aldehydes
  作者：Clément Mazet

  DOI：10.2533/chimia.2013.658

  日期：——

  The present article summarizes the development of two novel and complementary catalytic methods to access ?-chiral aldehydes. A C1-symmetric chiral (P,N) ligand with a structure derived from the ubiquitous binepine scaffold has been specifically designed for the Pd-catalyzed ?-arylation of aldehydes to access indane derivatives with a well-defined quaternary stereocenter in high yields and excellent enantioselectivities. In addition, a dinuclear palladium hydride catalyst has been synthesized for the isomerization of terminal and trisubstituted epoxides into aldehydes and ketones respectively. Combined experimental and theoretical investigations pointed to an unprecedented 'epoxide-opening/hydride-transfer' sequence. The mechanism also features two distinct enantio-determining steps in the kinetic resolution of racemic epoxides.

  本文总结了两种新颖且互补的催化方法的发展，用于获取α-手性醛类化合物。一种源自广泛存在的bipine桥架的C1对称手性（P,N）配体已经专门设计用于Pd催化的α-芳基化反应，以获得具有明确定义的四元手性中心的茚烷衍生物，产率高且选择性优异。此外，合成了一种双核钯氢化物催化剂，用于将末端和三取代环氧化物异构化为相应的醛和酮。结合实验和理论研究指出了一种前所未有的“环氧化物开环/氢转移”序列。该机制还包括在消旋环氧化物的动力学拆分过程中的两个不同的手性决定步骤。
• Enantioselective Hydrolysis of 2, 2-Disubstituted Oxiranes Mediated by Microsomal Epoxide Hydrolase
  作者：Deevi Basavaiah、Sarikonda Bhaskar Raju

  DOI：10.1080/00397919508013848

  日期：1995.11

  Abstract 2-Aryl-2-methyloxiranes are enantioselectively hydrolyzed with microsomal epoxide hydrolase from pig liver to provide 1, 2-diols containing a tertiary benzylic alcohol stereogenic centre upto 34% enantio-meric purities.

  摘要 2-Aryl-2-methyloxirane 用来自猪肝的微粒体环氧化物水解酶对映选择性水解，得到 1, 2-二醇，其中含有叔苄醇立体中心，对映体纯度高达 34%。
• The trading of space for time under weakly activated catalysis: expeditious synthesis of β-NH₂ alcohols <i>via</i> a direct ammonolysis of epoxides with ammonia
  作者：Guolan Ma、Chang Xu、Shaoxiong Yang、Yanren Zhu、Silei Ye、Rui Qin、Chongchong Zeng、Wenqiang Du、Hongbin Zhang、Jingbo Chen

  DOI：10.1039/d2gc04647d

  日期：——

  The direct synthesis of β-NH2 alcohols via flexible ammonolysis of epoxides is still a challenging and unresolved problem. Herein, we present a strategy of “trading space for time under weakly activated catalysis” and “shielding the reactivity of the product”, and thereby developed a novel single-step ammonolysis reaction of epoxides with ammonia. A stoichiometric amount of HCO2NH4 as an additive plays

  通过环氧化物的灵活氨解直接合成β-NH 2醇仍然是一个具有挑战性和未解决的问题。在此，我们提出了“在弱活化催化下以空间换时间”和“屏蔽产物的反应性”的策略，从而开发了一种新型的环氧化物与氨的一步氨解反应。化学计量的 HCO 2 NH 4作为添加剂在底物的整体活化和完全抑制过度烷基化的副反应中起着双重作用。范围广泛的底物，包括萜烯和类固醇衍生的环氧化物，干净地提供了目标 β-NH 2在易于调节的温和条件下，醇的产量从好到极好。此外，该合成方案不含金属且环保，可用于生物活性 β-NH 2醇的克级合成，这些醇可轻松转化为多种功能化分子。
• β-tert-Butyl aspartate as an organocatalyst for the asymmetric α-amination of α,α-disubstituted aldehydes
  作者：Alexis Theodorou、Giorgos N. Papadopoulos、Christoforos G. Kokotos

  DOI：10.1016/j.tet.2013.04.103

  日期：2013.7

  The enantioselective alpha-amination reaction of alpha,alpha-disubstituted aldehydes can lead to a variety of enantioenriched amino aldehydes, amino alcohols, and amino acids. After screening a variety of amino acids and their derivatives, we identified a cheap, simple, commercially available aspartic acid derivative that can catalyze efficiently the reaction between alpha,alpha-disubstituted aldehydes and dialkyl azodicarboxylates. The reaction proceeds smoothly leading to the corresponding alpha-aminated adducts in moderate to quantitative yields and moderate to high enantioselectivities (up to 96% ee). Finally, the conversion of these adducts to alpha,alpha-disubstituted quaternary amino acids is also described. 2013 Elsevier Ltd. All rights reserved.
• Sugai, Saburo; Kodama, Takashi; Akaboshi, Sanya, Chemical and pharmaceutical bulletin, 1984, vol. 32, # 1, p. 99 - 105
  作者：Sugai, Saburo、Kodama, Takashi、Akaboshi, Sanya、Ikegami, Shiro

  DOI：——

  日期：——