期刊
ACS OMEGA
卷 7, 期 10, 页码 8665-8674出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsomega.1c06664
关键词
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资金
- Czech Science Foundation [21-12924S]
- Charles University Grant Agency [1190218]
This study investigates the catalytic activation of C-C bonds in ring-strained compounds, followed by annulation to generate structurally more complex compounds. The location and selectivity of C-C bond activation were determined using a combination of computational predictions and experimental tests. Pentacyclic azaaromatic compounds were successfully synthesized using this approach.
C-C bond activation by transition metal complexes in ring-strained compounds followed by annulation with unsaturated compounds is an efficient approach to generate structurally more complex compounds. However, the site of catalytic C-C bond activation is difficult to predict in unsymmetrically substituted polycyclic systems. Here, we report a study on the (regio)selective catalytic cleavage of selected C-C bonds in 1-aza-[3]triphenylene, followed by annulation with alkynes, forming products with extended p-conjugated frameworks. Based on density functional theory (DFT) calculations, we established the stability of possible transition metal intermediates formed by oxidative addition to the C-C bond and thus identified the likely site of C-C bond activation. The computationally predicted selectivity was confirmed by the following experimental tests for the corresponding Ir-catalyzed C-C cleavage reaction followed by an alkyne insertion that yielded mixtures of two mono-insertion products isolated with yields of 34-36%, due to the close reactivity of two bonds during the first C-C bond activation. Similar results were obtained for twofold Ir- or Rh-catalyzed insertion reactions, with higher yields of 72-77%. In a broader context, by combining DFT calculations, which provided insights into the relative reactivity of individual C-C bonds, with experimental results, our approach allows us to synthesize previously unknown pentacyclic azaaromatic compounds.
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