Unraveling the flavin-catalyzed photooxidation of benzylic alcohol with transient absorption spectroscopy from sub-pico- to microseconds.

Flavin-mediated photooxidations have been described for applications in synthetic organic chemistry for some time and are claimed to be a route to the use of solar energy. We present a detailed investigation of the involved photophysical and photochemical steps in methoxybenzyl alcohol oxidation on a timescale ranging from sub-picoseconds to tens of microseconds. The results establish the flavin triplet state as the key intermediate for the photooxidation. The initial step is an electron transfer from the alcohol to the triplet state of the flavin catalyst with (3)k(ET)≈ 2 × 10(7) M(-1) s(-1), followed by a proton transfer in ∼6 µs. In contrast, the electron transfer involving the singlet state of flavin is a loss channel. It is followed by rapid charge recombination (τ = 50 ps) without significant product formation as seen when flavin is dissolved in pure benzylic alcohol. In dilute acetonitrile/water solutions of flavin and alcohol the electron transfer is mostly controlled by diffusion, though at high substrate concentrations >100 mM we also find a considerable contribution from preassociated flavin-alcohol-aggregates. The model including a productive triplet channel and a competing singlet loss channel is confirmed by the course of the photooxidation quantum yield as a function of substrate concentration: We find a maximum quantum yield of 3% at 25 mM of benzylic alcohol and significantly smaller values for both higher and lower alcohol concentrations. The observations indicate the importance to perform flavin photooxidations at optimized substrate concentrations to achieve high quantum efficiencies and provide directions for the design of flavin photocatalysts with improved performance.

Visible light flavin photo-oxidation of methylbenzenes, styrenes and phenylacetic acids.

We report the photocatalytic oxidation of benzylic carbon atoms under mild conditions using riboflavin tetraacetate as photocatalyst and blue-emitting LEDs (440 nm) as light source. Oxygen is the terminal oxidant and hydrogen peroxide appears as the only byproduct in most cases. The process oxidizes toluene derivatives, stilbenes, styrenes and phenylacetic acids to their corresponding benzaldehydes. A benzyl methyl ether and acylated benzyl amines are oxidized directly to the corresponding methyl ester or benzylimides. The mechanism of the reactions has been investigated and the results indicate that oxygen addition to benzyl radicals is a key step of the oxidation process in the case of phenylacetic acids.

Laboratory apparatus for the accurate, facile and rapid determination of visible light photoreaction quantum yields.

A novel setup for the direct determination of the quantum yield in photocatalytic and photochemical processes is reported. It combines the opto-electronic measurement of the absorbed amount of light with established quantitative chemical analysis of the products. High power visible LEDs are found to be convenient light sources for the illumination without the need for spectral filtering. The LED output can be imaged efficiently and in a controlled fashion into the sample. The residual transmitted light is continuously monitored by a dedicated and calibrated solar cell. The setup can be used under the conditions of a chemical synthesis laboratory. All information needed for the assembly and operation of the device is made available. The performance is validated by comparison to standard chemical actinometry and by the determination of quantum yields for reactions reported by others and ones investigated in our own laboratory.