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Secondary metabolites produced by bacteria and fungi represent a unique and valuable pool of natural chemical diversity, assembled from a multitude of individual and mixed biosynthetic pathways. These compounds, which often incorporate complex carbon and heterocyclic scaffolds, bristling with functionality and stereochemical complexity, have successfully inspired and informed the discovery and development of new pharmaceuticals, agrochemicals, and biomolecular tools for over a century. This chapter uses a number of noteworthy case studies to illustrate the important role played by nuclear magnetic resonance spectroscopy in the characterization and structure elucidation of microbial metabolites.

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