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A visible-light activated secondary phosphine oxide ligand enabling Pd-catalyzed radical cross-couplings.

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.

SUBMITTER: Kuribara T

PROVIDER: S-EPMC9279477 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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A visible-light activated secondary phosphine oxide ligand enabling Pd-catalyzed radical cross-couplings.

Kuribara Takahito T Nakajima Masaya M Nemoto Tetsuhiro T

Nature communications 20220713 1

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 t ...[more]

PMID: 35831306

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