Flavin Nitroalkane Oxidase Mimics Compatibility with NOx/TEMPO Catalysis: Aerobic Oxidization of Alcohols, Diols, and Ethers

Biomimetic flavin organocatalysts oxidize nitromethane to formaldehyde and NO_<i>x</i>providing a relatively nontoxic, noncaustic, and inexpensive source for catalytic NO₂ for aerobic TEMPO oxidations of alcohols, diols, and ethers. Alcohols were oxidized to aldehydes or ketones, cyclic ethers to esters, and terminal diols to lactones. In situ trapping of NO_<i>x</i> and formaldehyde suggest an oxidative Nef process reminiscent of flavoprotein nitroalkane oxidase reactivity, which is achieved by relatively stable 1,10-bridged flavins. The metal-free flavin/NO_x/TEMPO catalytic cycles are uniquely compatible, especially compared to other Nef and NO_x-generating processes, and reveal selectivity over flavin-catalyzed sulfoxide formation. Aliphatic ethers were oxidized by this method, as demonstrated by the conversion of (−)-ambroxide to (+)-sclareolide.