A Catalytic Alkylation of Ketones via sp3 C-H Bond Activation.
J Org Chem
; 88(10): 6333-6346, 2023 May 19.
Article
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| ID: mdl-35649206
ABSTRACT
We identified a ternary hybrid catalyst system composed of an acridinium photoredox catalyst, a thiophosphoric imide (TPI) catalyst, and a titanium complex catalyst that promoted an intermolecular addition reaction of organic molecules with various ketones through sp3 C-H bond activation. The thiyl radical generated via single-electron oxidation of TPI by the excited photoredox catalyst abstracted a hydrogen atom from organic molecules such as toluene, benzyl alcohol, alkenes, aldehydes, and THF. The thus-generated carbon-centered radical species underwent addition to ketones and aldehydes. This intrinsically unfavorable step was promoted by single-electron reduction of the intermediate alkoxy radical by catalytically generated titanium(III) species. This reaction provided an efficient and straightforward route to a broad range of tertiary alcohols and was successfully applied to late-stage functionalization of drugs or their derivatives. The proposed mechanism was supported by both experimental and theoretical studies.
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1
Colección:
01-internacional
Banco de datos:
MEDLINE
Idioma:
En
Revista:
J Org Chem
Año:
2023
Tipo del documento:
Article
País de afiliación:
Japón