Photocatalytic Oxygenation of Pivalic Acid with Molecular Oxygen via Photoinduced Electron Transfer using 10-Methylacridinium Ions

Abstract

Photoirradiation of the absorption band of the 10-methylacridinium ion (AcrH+) with visible light in deaerated CH3CN/H2O (1:1 v/v) containing pivalic acid (Bu(t)COOH) and less than 1 equiv of NaOH results in the selective formation of 9-tert-butyl-9,10-dihydro-10-methylacridine (AcrHBu(t)). The same product is obtained in O2-saturated CH3CN/H2O under visible light irradiation. Photoirradiation of the absorption band of AcrHBu(t) with UV light in deaerated CH3CN/H2O (1:1 v/v) results in the formation of tert-butyl hydroperoxide (Bu(t)OOH), accompanied by regeneration of AcrH+. This cycle can be repeated several times. When AcrH+ is replaced by the 9-phenyl derivative (AcrPh+), AcrPh+ acts as an effective photocatalyst for the one-pot photooxygenation of Bu(t)COOH in the presence of less than 1 equiv of NaOH relative to Bu(t)COOH with O2 to yield Bu(t)OOH and Bu(t)H. The photocatalytic oxygenation mechanism is discussed based on the detection of radical intermediates by laser flash photolysis and ESR measurements as well as quantum yield determination.