Computational, Mechanistic, and Experimental Insights into Regioselective Catalytic C–C Bond Activation in Linear 1-Aza-[3]triphenylene
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F22%3A10443831" target="_blank" >RIV/00216208:11310/22:10443831 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=cWfXFEa2pF" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=cWfXFEa2pF</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acsomega.1c06664" target="_blank" >10.1021/acsomega.1c06664</a>
Alternative languages
Result language
angličtina
Original language name
Computational, Mechanistic, and Experimental Insights into Regioselective Catalytic C–C Bond Activation in Linear 1-Aza-[3]triphenylene
Original language description
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.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10401 - Organic chemistry
Result continuities
Project
<a href="/en/project/GA21-29124S" target="_blank" >GA21-29124S: REAP and Other Catalytic Reactions in Synthesis of Nitrogen-Embbeded Polyaromatic Hydrocarbons</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2022
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
ACS Omega [online]
ISSN
2470-1343
e-ISSN
2470-1343
Volume of the periodical
7
Issue of the periodical within the volume
10
Country of publishing house
US - UNITED STATES
Number of pages
10
Pages from-to
8665-8674
UT code for WoS article
000783601100043
EID of the result in the Scopus database
2-s2.0-85126791866