在离散CuIII-Aryl复合物中形成C-N键
Maxwell S Reese1, Mitchell G Bonanno1, Jamey K Bower1
1Department of Chemistry & Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States.
研究人员合成并研究了新的铜 (III) 合体,揭示了铜催化C-N合反应和副产品形成机制的洞察力.
科学领域:
- 有机金属化学
- 催化剂
- 合成化学
背景情况:
- 铜 (III) 类是铜催化键形成的关键但不太了解的中间体.
- 离散的Cu(III) -Ar复合物的稀有性阻碍了对C-异原子键形成和副产品生成 (Ar-H,Ar-Ar) 的机制研究.
研究的目的:
- 合成和描述新的铜 (II) 和铜 (III) 复合物.
- 研究这些复合体在C-N合反应中的反应性.
- 阐明铜催化反应中的副产品形成机制.
主要方法:
- 使用各种基供体 (ZnAr2R,TMS-ArR,ArRBpin) 合成铜(II) 基复合物 ([TBA][LCuII-ArR]).
- 氧化铜 (II) 复合物以产生铜 (III) 烯复合物 (LCuIII-ArR).
- 铜 (III) 复合物与核友的反应,然后进行哈梅特分析.
主要成果:
- 一系列模仿反应中间体的Cu (II) 和Cu (III) 烯复合物的成功合成.
- 除了Ar-H和Ar-Ar副产品外,还获得了高达64%的C-N合产品.
- 哈梅特分析 (ρ = -1.66) 表明LCuIII-ArR的电友性,支持提出的反应机制.
结论:
- 这项研究提供了第一个与C-N合相关的离散Cu (III) - 合物.
- 建议在铜催化合反应中形成Ar-H和Ar-Ar副产品的机制.
- 这些发现提供了对铜催化C-异原子键形成的机理方面的关键见解.
更多相关视频
10:51The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
07:20Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
相关概念视频
Valence Bond Theory
Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview
¹H NMR: Long-Range Coupling
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
Electrophilic Addition to Alkynes: Halogenation
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Aromatic Hydrocarbon Cations: Structural Overview
Removing one hydrogen from the intervening CH2 group...
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
