Probing hyperconjugative aromaticity in 2H-pyrrolium and cyclopentadiene containing Group 9 transition metal substituent: Bridged carbonyl ligands can enhance aromaticity

Author(s):  
Jie Zeng ◽  
Yu Zhao ◽  
Fangzhou Xu ◽  
Jun Zhu

Aromaticity and hyperconjugation are two fundamental concepts in organic chemistry. By combination of the two concepts together, the resulting hyperconjugative aromaticity has attracted considerable attention from both theoretical and computational...

Author(s):  
Long Yang ◽  
Wuxin Zhou ◽  
Qiang Li ◽  
Xiangge Zhou

Carbon−carbon bond activation is one of the most challenging and important research areas in organic chemistry. Selective C−C bond activation of unstrained substrates is difficult to achieve owing to its...


2019 ◽  
Vol 55 (87) ◽  
pp. 13048-13065 ◽  
Author(s):  
Ming Zhang ◽  
Qiuhong Wang ◽  
Yiyuan Peng ◽  
Zhiyuan Chen ◽  
Changfeng Wan ◽  
...  

Nitrogen heterocycles are of great medicinal importance, and the construction of nitrogen heterocyclic scaffolds has been one of the focuses in synthetic organic chemistry.


2019 ◽  
Vol 91 (4) ◽  
pp. 563-573 ◽  
Author(s):  
Marta Gozzi ◽  
Benedikt Schwarze ◽  
Evamarie Hey-Hawkins

Abstract Today, medicinal chemistry is still clearly dominated by organic chemistry, and commercially available boron-based drugs are rare. In contrast to hydrocarbons, boranes prefer the formation of polyhedral clusters via delocalized 3c2e bonds, such as polyhedral dicarba-closo-dodecaborane(12) (closo-C2B10H12). These clusters have remarkable biological stability, and the three isomers, 1,2- (ortho), 1,7- (meta), and 1,12-dicarba-closo-dodecaborane(12) (para), have attracted much interest due to their unique structural features. Furthermore, anionic nido clusters ([7,8-C2B9H11]2−), derived from the neutral icosahedral closo cluster 1,2-dicarba-closo-dodecaborane(12) by deboronation followed by deprotonation are suitable ligands for transition metals and offer the possibility to form metallacarboranes, for example via coordination through the upper pentagonal face of the cluster. The isolobal analogy between the cyclopentadienyl(–1) ligand (Cp−) and [C2B9H11]2− clusters (dicarbollide anion, Cb2−) is the motivation in using Cb2− as ligand for coordination to a metal center to design compounds for various applications. This review focuses on potential applications of half- and mixed-sandwich-type transition metal complexes in medicine.


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