DFT Study of Selectivity in Photoelectrocatalytic C–H Arene Aminations
Location
Science Center Perlik Commons
Document Type
Poster - Open Access
Start Date
5-13-2022 12:00 PM
End Date
5-13-2022 2:00 PM
Abstract
The topic of photoelectrocatalytic (PEC) C-H amination of arenes is important to the scientific community because of the clear benefits for sustainability and drug synthesis. The purpose of this study was to explain the regioselectivity of C–N bond formation in the photoelectrocatalytic C–H amination of arenes.. Generally, the para isomer is expected to dominate, but Zhang et al. (2019) presented an uncommon case with high ortho selectivity. Thus, the goal of our study was to understand why this is taking place and how the newer methods stray away from the normal para selectivity. We used Density Functional Theory (DFT) calculations to study the transition states forming the C–N bonds..When the transition state energies of C–N bond formation at different positions of the aromatic ring were compared, the lowest energy transition state was the ortho, in good agreement with the experimental observation that ortho is the major product. We also found that C–N formation at the meta position is the least preferred. Future work will focus on locating more possible variations of the transition states and studying the role of hexafluoroisopropanol (HFIP) solvent.
Keywords:
Computational chemistry, Arene aminations, Photoelectrocatalysis
Recommended Citation
Bielinksi Leitão, Sofia; Ortíz, Ophelia; and Rekate, Emma, "DFT Study of Selectivity in Photoelectrocatalytic C–H Arene Aminations" (2022). Research Symposium. 3.
https://digitalcommons.oberlin.edu/researchsymp/2022/posters/3
Major
Chemistry and Biochemistry
Award
STRONG
Project Mentor(s)
Shuming Chen, Chemistry
2022
DFT Study of Selectivity in Photoelectrocatalytic C–H Arene Aminations
Science Center Perlik Commons
The topic of photoelectrocatalytic (PEC) C-H amination of arenes is important to the scientific community because of the clear benefits for sustainability and drug synthesis. The purpose of this study was to explain the regioselectivity of C–N bond formation in the photoelectrocatalytic C–H amination of arenes.. Generally, the para isomer is expected to dominate, but Zhang et al. (2019) presented an uncommon case with high ortho selectivity. Thus, the goal of our study was to understand why this is taking place and how the newer methods stray away from the normal para selectivity. We used Density Functional Theory (DFT) calculations to study the transition states forming the C–N bonds..When the transition state energies of C–N bond formation at different positions of the aromatic ring were compared, the lowest energy transition state was the ortho, in good agreement with the experimental observation that ortho is the major product. We also found that C–N formation at the meta position is the least preferred. Future work will focus on locating more possible variations of the transition states and studying the role of hexafluoroisopropanol (HFIP) solvent.
Notes
Presenters: Ophelia Ortíz and Sofia Bielinski Leitão