The present feature article details our endeavors towards the synthesis of the highly intricate bisindole alkaloid bipleiophylline and its biosynthetic precursor voacalgine A: from the development of a divergent oxidative coupling between indole and dihydroxybenzoic acids, to the exploration of the chemical space from natural products and culminating in the biomimetic assembly of voacalgine A and bipleiophylline.
From structure, to labelling, biomimetic synthesis and mechanism, to gene clusters and engineering, the metabolites discovered by Harold Raistrick remain at the forefront of progress in fungal biosynthesis.