Second-generation probes for biosynthetic intermediate capture: towards a comprehensive profiling of polyketide assembly

Malonyl carba(dethia) N -decanoyl cysteamine methyl esters and novel acetoxymethyl esters were utilised as second-generation probes for polyketide intermediate capture. The use of these tools in vivo led to the characterisation of an almost complete set of biosynthetic intermediates from a modular assembly line, providing a first kinetic overview of intermediate processing leading to complex natural product formation. Novel chemical probes provide kinetic insights into polyketide assembly.