Computational, Mechanistic, and Experimental Insights into Regioselective Catalytic C–C Bond Activation in Linear 1-Aza-[3]triphenylene

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Computational, Mechanistic, and Experimental Insights into Regioselective Catalytic C–C Bond Activation in Linear 1-Aza-[3]triphenylene

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Computational, Mechanistic, and Experimental Insights into Regioselective Catalytic C–C Bond Activation in Linear 1-Aza-[3]triphenylene

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA21-29124S" target="_blank" >GA21-29124S: REAP a další katalytické reakce pro syntézu azapolyaromatických uhlovodíků</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2022

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

ACS Omega [online]

ISSN

2470-1343

e-ISSN

2470-1343

Svazek periodika

7

Číslo periodika v rámci svazku

10

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

8665-8674

Kód UT WoS článku

000783601100043

EID výsledku v databázi Scopus

2-s2.0-85126791866