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

Result code in 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>
Result on the web
<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>

Result language
angličtina
Original language name
Catalyst-Counterion Controlled, Regioselective C-C Bond Cleavage in 1-Azabiphenylene: Synthesis of Selectively Substituted Benzoisoquinolines
Original language description
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.
Czech name
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Czech description
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Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10401 - Organic chemistry

Project
<a href="/en/project/GA17-07707S" target="_blank" >GA17-07707S: Development of New Syntheses of Azaheterocycles</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year
2018
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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