Journal article
Wavelength-Selective Reactivity of Iron(III) Halide Salts in Photocatalytic C-H Functionalization
Journal of organic chemistry, Vol.90(9), pp.3404-3411
03/07/2025
DOI: 10.1021/acs.joc.4c03107
PMCID: PMC11894668
PMID: 39993181
Appears in UI Libraries Support Open Access
Abstract
The utility of halogen radicals in hydrocarbon functionalization extends from early examples of photochemical halogenation to recent reports using photoredox catalysis with iridium complexes and simple transition metal salts such as FeCl
. The majority of these methods (uncatalyzed and iron-catalyzed) require UV light (λ ≤ 390 nm), and systematic efforts to enable the use of visible light remain valuable. We report the use of a simple Fe(III) salt that enables a C-H to C-C and C-N functionalization under visible light. The reactivity and selectivity profile using different light sources demonstrates wavelength-selective behavior, which was further investigated with deuterium kinetic isotope effect experiments and DFT calculations. These results show that control over the reactive intermediates in this iron-catalyzed reaction can be achieved through proper choice of the wavelength of irradiation.
Details
- Title: Subtitle
- Wavelength-Selective Reactivity of Iron(III) Halide Salts in Photocatalytic C-H Functionalization
- Creators
- Cory T Ludwig - University of IowaIsiaka A Owolabi - University of IowaLogan W Evans - University of IowaGabriel J Smith - Michigan State UniversityAlexander Ramos - University of IowaJames J Shepherd - Michigan State UniversityDavid B C Martin - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Journal of organic chemistry, Vol.90(9), pp.3404-3411
- DOI
- 10.1021/acs.joc.4c03107
- PMID
- 39993181
- PMCID
- PMC11894668
- NLM abbreviation
- J Org Chem
- ISSN
- 0022-3263
- eISSN
- 1520-6904
- Publisher
- American Chemical Society
- Grant note
- National Institute of General Medical Sciences: S10-RR025500 NIH: CHE-1952860 NSF CAREER: DE-SC0021317 University of Iowa - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences Early Career Research Program (ECRP): CHE-1919422 NSFUniversity of Iowa
This work was supported by NIH R35 GM138050 (to D.B.C.M.), NSF CAREER CHE-1952860 (to D.B.C.M.), and start-up funds from the University of Iowa. The computational research (G.J.S., J.J.S.) was funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences Early Career Research Program (ECRP) under Award Number DE-SC0021317 (to J.J.S). NMR instrumentation for this research was supported by funding from the NIH (S10-RR025500), the NSF (CHE-2017828), and the University of Iowa. Mass spectrometry instrumentation for this research was supported by funding from the NSF (CHE-1919422) and the University of Iowa. J.J.S. gratefully acknowledges Prof. Katharine Moore Tibbetts for helpful discussion.
- Language
- English
- Electronic publication date
- 02/24/2025
- Date published
- 03/07/2025
- Academic Unit
- Iowa Neuroscience Institute; Chemistry
- Record Identifier
- 9984795472002771
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