This work describes our computational study of substituent effects on the formation and cyclization of 2′-arylbenzaldehyde and 2′-arylacetophenone oxime ether radical cations. Recent experimental work by de Lijser and co-workers has demonstrated that these reactive intermediates, which are generated through photoinduced electron transfer (PET) with a photosensitizer, undergo intramolecular cyclization to yield substituted phenanthridines. The experimental study further showed correlations between the yield of cyclized products and the Hammett σ Para + parameter of the substituent on the aryl group, with both strongly electronwithdrawing and electron-donating substituents shown to significantly reduce the product yield. By analyzing the ΔG PET associated with radical cation formation as well as the thermodynamics and kinetics of radical cation cyclization, we provide an explanation for these observations. We then computationally extend this mechanistic analysis to 2′-arylbenzaldehyde oxime ethers with substituents also present on the central benzene ring and show that such substituents generally have a larger impact on the PET-induced cyclization than those on the aryl group. Overall, this work extends our understanding of the overall scope of this photooxidative route toward substituted phenanthridines as well as makes clear predictions as to how the formation of oxime ether radical cations can be tuned by substituents.
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