Artificial Biosynthetic Pathway for an Unnatural Terpenoid with an Iridiumcontaining P450

This is the authors' abstract. We don't add key points for this paper.

Synthetic biology enables microbial hosts to produce complex molecules that are otherwise produced by organisms that are rare or difficult to cultivate, but the structures of these molecules are limited to chemical reactions catalyzed by natural enzymes. The integration of artificial metalloenzymes (ArMs) that catalyze abiotic reactions into metabolic networks could broaden the cache of molecules produced biosynthetically by microorgansms. We report the assembly of an ArM containing an iridium-porphyrin complex in the cytoplasm of a terpene producing Escherichia coli by a heterologous heme transport machinery, and insertion of this ArM into a natural biosynthetic pathway to produce an unnatural terpenoid. This work shows that synthetic biology and synthetic chemistry, incorporated together in whole cells, can produce molecules previously inaccessible to nature.