In-insect synthesis of oxygen-doped molecular nanocarbons.

Abstract

Many functional molecules and materials have been produced with organic chemistry or with in vitro enzymatic approaches. Individual organisms, such as insects, have the potential to serve as natural reaction platforms in which high densities of multiple enzymes can perform new and complex reactions. We report an "in-insect" unnatural product synthesis that takes advantage of their xenobiotic metabolism. We selectively transform belt- and ring-shaped molecular nanocarbons into otherwise difficult-to-prepare derivatives in which oxygen atoms are inserted into aromatic rings. Cytochrome P450 variants are most likely the enzymes responsible for this reaction. Molecular dynamics simulations and quantum chemical calculations indicated a possible mode of substrate incorporation into the enzyme and an unconventional mechanism of direct oxygen insertion into carbon-carbon bonds.