Unconventional Biocatalytic Strategies Orchestrate the Synthesis of the Nucleoside Analog Sinefungin.
In vitro and in vivo analyses support a recent finding that the defining carbon-carbon bond is formed not by a long-hypothesized PLP-dependent process, but by a vitamin B12-dependent radical SAM enzyme, and expand upon the current knowledge of radical-mediated C-C bond formation and PEARL enzyme catalysis.