Catalyst-Counterion Controlled, Regioselective C-C Bond Cleavage in 1-Azabiphenylene: Synthesis of Selectively Substituted Benzoisoquinolines

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F18%3A10384281" target="_blank" >RIV/00216208:11310/18:10384281 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1021/acscatal.8b01874" target="_blank" >https://doi.org/10.1021/acscatal.8b01874</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acscatal.8b01874" target="_blank" >10.1021/acscatal.8b01874</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Catalyst-Counterion Controlled, Regioselective C-C Bond Cleavage in 1-Azabiphenylene: Synthesis of Selectively Substituted Benzoisoquinolines

Popis výsledku v původním jazyce

Catalytic C-C bond cleavage processes followed by further transformations are some of the most fascinating reactions in chemistry and valuable organic synthesis tools. Herein, we demonstrate that the regioselectivity of C-C bond cleavage in 1-azabiphenylene and its derivatives can be switched by using neutral or cationic transition metal catalysts. The use of the former leads to selective distal C-C bond cleavage (with respect to the position of the nitrogen atom), whereas use of the latter leads to selective proximal bond cleavage. This process enables synthesis of a variety of complex heterocycles by regioselective C-C bond cleavage switched on demand. Density functional theory calculations (SMD/M06/DGDZVP level of theory) show that the regioselectivity is a result of kinetically controlled oxidative addition into the C-C bond. In neutral complexes the transition states (TS) for distal cleavage have lower energy, in agreement with experiments. For the cationic catalyst, the proximal TSs are stabilized presumably by relieving the Cl-N dipole dipole repulsion when the Rh-bound Cl is removed whereas the distal TSs remain largely unaffected.

Název v anglickém jazyce

Catalyst-Counterion Controlled, Regioselective C-C Bond Cleavage in 1-Azabiphenylene: Synthesis of Selectively Substituted Benzoisoquinolines

Popis výsledku anglicky

Catalytic C-C bond cleavage processes followed by further transformations are some of the most fascinating reactions in chemistry and valuable organic synthesis tools. Herein, we demonstrate that the regioselectivity of C-C bond cleavage in 1-azabiphenylene and its derivatives can be switched by using neutral or cationic transition metal catalysts. The use of the former leads to selective distal C-C bond cleavage (with respect to the position of the nitrogen atom), whereas use of the latter leads to selective proximal bond cleavage. This process enables synthesis of a variety of complex heterocycles by regioselective C-C bond cleavage switched on demand. Density functional theory calculations (SMD/M06/DGDZVP level of theory) show that the regioselectivity is a result of kinetically controlled oxidative addition into the C-C bond. In neutral complexes the transition states (TS) for distal cleavage have lower energy, in agreement with experiments. For the cationic catalyst, the proximal TSs are stabilized presumably by relieving the Cl-N dipole dipole repulsion when the Rh-bound Cl is removed whereas the distal TSs remain largely unaffected.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA17-07707S" target="_blank" >GA17-07707S: Vývoj nových syntéz azaheterocyklů</a><br>

Návaznosti

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

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

ACS Catalysis

ISSN

2155-5435

e-ISSN

—

Svazek periodika

8

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

10290-10299

Kód UT WoS článku

000449723900041

EID výsledku v databázi Scopus

2-s2.0-85054811423