School of Chemistry - Research Publications

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Author: Polyzos, Anastasios × Author: Czyz, Milena × End date: 2022 ×

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    Auxiliary-Directed C(sp3)-H Arylation by Synergistic Photoredox and Palladium Catalysis
    Czyz, ML ; Lupton, DW ; Polyzos, A (WILEY-V C H VERLAG GMBH, 2017-10-17)
    Herein we describe the auxiliary-directed arylation of unactivated C(sp3 )-H bonds with aryldiazonium salts, which proceeds under synergistic photoredox and palladium catalysis. The site-selective arylation of aliphatic amides with α-quaternary centres is achieved with high selectivity for β-methyl C(sp3 )-H bonds. This operationally simple method is compatible with carbocyclic amides, a range of aryldiazonium salts and proceeds at ambient conditions.
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    Photoexcited Pd(ii) auxiliaries enable light-induced control in C(sp3)-H bond functionalisation
    Czyz, ML ; Weragoda, GK ; Horngren, TH ; Connell, TU ; Gomez, D ; O'Hair, RAJ ; Polyzos, A (ROYAL SOC CHEMISTRY, 2020-03-07)
    Herein we report the photophysical and photochemical properties of palladacycle complexes derived from 8-aminoquinoline ligands, commonly used auxiliaries in C-H activation. Spectroscopic, electrochemical and computational studies reveal that visible light irradiation induces a mixed LLCT/MLCT charge transfer providing access to synthetically relevant Pd(iii)/Pd(iv) redox couples. The Pd(ii) complex undergoes photoinduced electron transfer with alkyl halides generating C(sp3)-H halogenation products rather than C-C bond adducts. Online photochemical ESI-MS analysis implicates participation of a mononuclear Pd(iii) species which promotes C-X bond formation via a distinct Pd(iii)/Pd(iv) pathway. To demonstrate the synthetic utility, we developed a general method for inert C(sp3)-H bond bromination, chlorination and iodination with alkyl halides. This new strategy in auxiliary-directed C-H activation provides predictable and controllable access to distinct reactivity pathways proceeding via Pd(iii)/Pd(iv) redox couples induced by visible light irradiation.