Natural products constitute a rich and highly diverse source of pharmaceuticals and agrochemicals, hence the detailed elucidation of biosynthetic pathways is of the utmost priority in view of novel synthetic biology for natural product production. In our lab we have been developing chemical probes for the capture and the characterization of natural product biosynthetic intermediates: for instance, we have extensively reported the use of nonhydrolysable mimics of acyl carrier protein-bound malonate units to off-load ketosynthase-bound biosynthetic intermediates during polyketide assembly in vitro and in vivo. These tools have allowed us to gain direct insights into polyketide pathways of various complexity, and, more recently, to generate ‘unnatural’ products comprising novel structural motifs for further chemoenzymatic modifications. Herein I will present and discuss our latest tool development and application for natural product biosynthetic investigations, including novel probes for the investigation of nonribosomal peptide biocatalysis (Figure 1) and preliminary insights into unusual polyketide-nonribosomal peptide assemblies.

Chemical probes for the investigation of natural product assembly: Biosynthetic insights and novel opportunities

253rd National Meeting (2017)

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