双(2-甲基苯基)甲基溴 | 60973-62-8

• 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: 双(2-甲基苯基)甲基溴
• 英文名称: 2,2'-(bromomethylene)bis(methylbenzene)
• 英文别名: 1,1'-(Bromomethylene)bis(2-methylbenzene)；1-[bromo-(2-methylphenyl)methyl]-2-methylbenzene
• CAS: 60973-62-8
• 化学式: C₁₅H₁₅Br
• 分子量: 275.188
• InChiKey: NLMHDZOMLKSFKM-UHFFFAOYSA-N

物化性质

• 沸点：
  142-144 °C(Press: 4 Torr)
• 密度：
  1.278±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  双(2-甲基苯基)甲基溴 在 potassium carbonate 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 111.5h， 生成 (4R,5R)-4,5-di(tert-butyl)-1-(bis(2-methylphenyl)methyl)-3-methylimidazolidin-2-ylidene copper(I) chloride
  参考文献：
  名称：

  Synthesis of Chiral C 1-Symmetric N-Heterocyclic Carbene Ligands: Application toward Copper-Catalyzed Homocoupling of 2-Naphthols

  摘要：

  Novel chiral C-1-symmetric NHC ligands can be prepared via dialkylation of chiral imidazoline scaffolds. Asymmetry in the ligand/metal complexes results from a chiral relay effect. The C-1-symmetric nature of the NHC ligand was proposed to allow for improved reactivity versus other achiral and chiral NHC complexes. The benefit of such ligands was demonstrated in copper-catalyzed oxidative coupling reactions.

  DOI：

  10.1055/s-0033-1338564
• 作为产物：
  描述：

  bis(2-methylphenyl)methanol 在 三溴化磷 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 以86%的产率得到双(2-甲基苯基)甲基溴
  参考文献：
  名称：

  Synthesis of Chiral C 1-Symmetric N-Heterocyclic Carbene Ligands: Application toward Copper-Catalyzed Homocoupling of 2-Naphthols

  摘要：

  Novel chiral C-1-symmetric NHC ligands can be prepared via dialkylation of chiral imidazoline scaffolds. Asymmetry in the ligand/metal complexes results from a chiral relay effect. The C-1-symmetric nature of the NHC ligand was proposed to allow for improved reactivity versus other achiral and chiral NHC complexes. The benefit of such ligands was demonstrated in copper-catalyzed oxidative coupling reactions.

  DOI：

  10.1055/s-0033-1338564

文献信息

• SYNTHESIS AND APPLICATION OF CHIRAL SUBSTITUTED POLYVINYLPYRROLIDINONES
  申请人：Kansas State University Research Foundation

  公开号：US20200306737A1

  公开（公告）日：2020-10-01

  Chiral polyvinylpyrrolidinone (CSPVP), complexes of CSPVP with a core species, such as a metallic nanocluster catalyst, and enantioselective oxidation reactions utilizing such complexes are disclosed. The CSPVP complexes can be used in asymmetric oxidation of diols, enantioselective oxidation of alkenes, and carbon-carbon bond forming reactions, for example. The CSPVP can also be complexed with biomolecules such as proteins, DNA, and RNA, and used as nanocarriers for siRNA or dsRNA delivery.

  手性聚乙烯吡咯烷酮（CSPVP），CSPVP与金属纳米团簇催化剂等核心物种形成的络合物，以及利用这种络合物进行对映选择氧化反应的方法被揭示。CSPVP络合物可用于不对称二醇氧化、烯烃对映选择氧化以及碳-碳键形成反应等。CSPVP还可以与蛋白质、DNA和RNA等生物分子形成络合物，并用作siRNA或dsRNA传递的纳米载体。
• Chiral Bifunctional Phosphine-Carboxylate Ligands for Palladium(0)-Catalyzed Enantioselective C−H Arylation
  作者：Lei Yang、Markus Neuburger、Olivier Baudoin

  DOI：10.1002/anie.201712061

  日期：2018.1.26

  Previous enantioselective Pd0‐catalyzed C−H activation reactions proceeding via the concerted metalation‐deprotonation mechanism employed either a chiral ancillary ligand, a chiral base, or a bimolecular mixture thereof. This study describes the development of new chiral bifunctional ligands based on a binaphthyl scaffold which incorporates both a phosphine and a carboxylic acid moiety. The optimal

  先前的对映选择性Pd 0催化的CH活化反应是通过手性辅助配体，手性碱或它们的双分子混合物通过一致的金属化-去质子化机理进行的。这项研究描述了基于双萘基支架的新手性双功能配体的开发，该萘并膦既包含膦又包含羧酸部分。最佳配体为解对称的C（sp 2）-H芳基化反应提供了高收率和对映选择性，从而导致5,6-二氢菲啶，而相应的单官能配体显示出低对映选择性。事实证明，该双功能体系适用于一系列取代的二氢菲啶，并允许消旋底物的平行动力学拆分。
• Chiral Diarylmethanes via Copper-Catalyzed Asymmetric Allylic Arylation with Organolithium Compounds
  作者：Sureshbabu Guduguntla、Valentín Hornillos、Romain Tessier、Martín Fañanás-Mastral、Ben L. Feringa

  DOI：10.1021/acs.orglett.5b03396

  日期：2016.1.15

  A highly enantioselective copper/N-heterocyclic carbene catalyzed allylic arylation with organolithium compounds is presented. The use of commercial or readily prepared aryllithium reagents in the reaction with allyl bromides affords a variety of chiral diarylvinylmethanes, comprising a privileged structural motif in pharmaceuticals, in high yields with good to excellent regio- and enantioselectivities

  提出了高度对映选择性的铜/ N-杂环卡宾与有机锂化合物的烯丙基芳基化反应。在与烯丙基溴的反应中使用市售或易于制备的芳基锂试剂可提供高收率的多种手性二芳基乙烯基甲烷，其在药物中具有优先的结构基序，具有良好或优异的区域和对映选择性。市售药物托特罗定（Detrol）的正式合成中说明了这种新转变的多功能性。
• The discovery of tropane derivatives as nociceptin receptor ligands for the management of cough and anxiety
  作者：Ginny D. Ho、John Anthes、Ana Bercovici、John P. Caldwell、Kuo-Chi Cheng、Xiaoming Cui、Ahmad Fawzi、Xiomara Fernandez、William J. Greenlee、John Hey、Walter Korfmacher、Sherry X. Lu、Robbie L. McLeod、Fay Ng、April Smith Torhan、Zheng Tan、Deen Tulshian、Geoffrey B. Varty、Xiaoying Xu、Hongtao Zhang

  DOI：10.1016/j.bmcl.2009.03.031

  日期：2009.5

  has led to the synthesis of a series of tropane (8-methyl-8-azabicyclo[3.2.1]octane) derivatives as optimized ligands. These compounds exhibit high affinity for the nociceptin receptor, moderate to excellent selectivity over the opioid μ receptor, and behave as full agonists. In this Letter, we present the synthesis and highlight the structure–activity relationship of tropane derivatives culminating in

  1作为Nociceptin受体的高亲和力配体的发现导致合成了一系列作为优化配体的托烷（8-甲基-8-氮杂双环[3.2.1]辛烷）衍生物。这些化合物对伤害感受器受体具有高亲和力，对阿片样物质μ受体的选择性中等至极好，并且表现为完全激动剂。在这封信中，我们介绍了合成方法并强调了托烷衍生物的结构-活性关系，最终确定了24和32为有效和口服活性的镇咳药和抗焦虑药。公开了预测人中潜在的3A4诱导的体外和体内活性，药代动力学概况和hPXR活性。
• Efficient Chiral N-Heterocyclic Carbene/Copper(I)-Catalyzed Asymmetric Allylic Arylation with Aryl Grignard Reagents
  作者：Khalid B. Selim、Yasumasa Matsumoto、Ken-ichi Yamada、Kiyoshi Tomioka

  DOI：10.1002/anie.200904676

  日期：2009.11.2

  Gamma rules: The title reaction was achieved in a highly regioselective manner using aryl Grignard reagents with monodentate chiral N‐heterocyclic carbene–copper(I) catalyst to give diarylvinylmethanes with excellent enantiomeric excess in excellent yield (see scheme).

  伽玛规则：使用芳基格氏试剂与单齿手性N-杂环卡宾-铜（I）催化剂，以高度区域选择性的方式实现标题反应，从而以极佳的收率得到对映体过量的二芳基乙烯基甲烷（参见方案）。