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- Title
A visible-light activated secondary phosphine oxide ligand enabling Pd-catalyzed radical cross-couplings.
- Authors
Kuribara, Takahito; Nakajima, Masaya; Nemoto, Tetsuhiro
- Abstract
Although transition metal-catalyzed reactions have evolved with ligand development, ligand design for palladium-catalyzed photoreactions remains less explored. Here, we report a secondary phosphine oxide ligand bearing a visible-light sensitization moiety and apply it to Pd-catalyzed radical cross-coupling reactions. The tautomeric phosphinous acid coordinates to palladium in situ, allowing for pseudo-intramolecular single-electron transfer between the ligand and palladium. Molecular design of the metal complexes aided by time-dependent density functional theory calculations enables the involvement of allyl radicals from π-allyl palladium(II) complexes, and alkyl and aryl radicals from the corresponding halides and palladium(0) complex. This complex enables radical cross-couplings by ligand-to-Pd(II) and Pd(0)-to-ligand single-electron transfer under visible-light irradiation. Ligand design is key for improving the performance in light-enabled catalytic processes. Here, the authors report the synthesis of a visible-light–activated secondary phosphine oxide ligand and apply it to Pd-catalyzed radical cross-coupling reactions.
- Subjects
PHOSPHINE oxides; TIME-dependent density functional theory; ARYL radicals; ALKYL radicals; ORGANIC conductors; ALLYL group
- Publication
Nature Communications, 2022, Vol 13, Issue 1, p1
- ISSN
2041-1723
- Publication type
Article
- DOI
10.1038/s41467-022-31613-9