Superiority of Iridium Photocatalyst and Role of Quinuclidine in Selective α-C(sp3)–H Alkylation: Theoretical Insights
- 9 December 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 86 (1), 484-492
- https://doi.org/10.1021/acs.joc.0c02227
Abstract
Recent experimental work reported that visible-light photoredox catalysis coupled with primary sulfonamides and electron-deficient alkenes could efficiently construct C–C bonds at the α-position of primary amine derivatives under mild conditions. Here, a systematic study was conducted to explore the non-negligible excited-state single-electron-transfer (SET) processes and the catalytic cycle. Hydrogen atom transfer (HAT) catalysis containing different site-selective functionalization, involved as a critical process during the reaction, was computationally characterized. The superiorities of iridium-based photoredox catalysts in terms of photoabsorption properties, phosphorescence rates, and electron-transfer rates for SET processes were focused on. In addition, the function of quinuclidine in the entire photocatalytic reaction was also probed. These intrinsic properties and detailed insights into the mechanism are supposed to be helpful to the understanding of the C–C bond functionalization reaction and the future application of the iridium-based photoredox catalyst.Keywords
Funding Information
- Ministry of Education of the People's Republic of China (2412018ZD006)
- National Natural Science Foundation of China (21673036, 21771035)
This publication has 55 references indexed in Scilit:
- Discovery of an α-Amino C–H Arylation Reaction Using the Strategy of Accelerated SerendipityScience, 2011
- A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-PuThe Journal of Chemical Physics, 2010
- Density Functionals with Broad Applicability in ChemistryAccounts of Chemical Research, 2008
- Semiempirical GGA‐type density functional constructed with a long‐range dispersion correctionJournal of Computational Chemistry, 2006
- Development of density functionals for thermochemical kineticsThe Journal of Chemical Physics, 2004
- Chemistry with ADFJournal of Computational Chemistry, 2001
- Generalized Gradient Approximation Made SimplePhysical Review Letters, 1996
- Stereoelectronic effects in intramolecular long-distance electron transfer in radical anions as predicted by ab-initio MO calculationsJournal of the American Chemical Society, 1986
- Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitalsThe Journal of Chemical Physics, 1985
- Formulation of the reaction coordinateThe Journal of Physical Chemistry, 1970