Photoexcitation of (diarylmethylene)amino benziodoxolones for alkylamination of styrene derivatives with carboxylic acids

• Published in: Chemical science (Cambridge) Vol. 15; no. 3; pp. 168 - 176
• Main Authors: Okumatsu, Daichi, Kiyokawa, Kensuke, Bao Nguyen, Linh Tran, Abe, Manabu, Minakata, Satoshi
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 17.01.2024; Royal Society of Chemistry; The Royal Society of Chemistry
• Subjects: Absorption spectroscopy; Amines; Carboxylates; Carboxylic acids; Chemistry; Chemistry, Multidisciplinary; Flash photolysis; Oxidation; Oxidizing agents; Photochemical reactions; Photoexcitation; Physical Sciences; Reagents; Science & Technology; Single electrons; Substrates; CENTERED RADICALS; OXIDATION; ALKENES; 1,2-CARBOAMINATION; SYN-CARBOAMINATION; CATALYZED 3-COMPONENT CARBOAMINATION; AMINO; ALKYLATION; INTERMOLECULAR CARBOAMINATION; C-H ACTIVATION
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d3sc06090j

The alkylamination of alkenes using pristine carboxylic acids was achieved by the photoexcitation of (diarylmethylene)amino benziodoxolones (DABXs), which serve as both an oxidant and an aminating reagent (an iminyl radical precursor). The developed method is a simple photochemical reaction without the need for external photosensitizers and shows a broad substrate scope for aliphatic carboxylic acids leading to the formation of primary, secondary, and tertiary alkyl radicals, thus enabling the facile synthesis of various structurally complex amines. Mechanistic investigations including transient absorption spectroscopy measurements using a laser flash photolysis (LFP) method disclosed the unique photochemical reactivity of DABXs, which undergoes homolysis of their I-N bonds to give an iminyl radical and ortho -iodobenzoyloxy radical, the latter of which participates in the single-electron oxidation of carboxylates. The alkylamination of alkenes using carboxylic acids was achieved by the photoexcitation of (diarylmethylene)amino benziodoxolones, which serve as both an oxidant and an aminating reagent.