Biosynthesis‐Assisted Structural Elucidation of the Bartolosides,Chlorinated Aromatic Glycolipids from Cyanobacteria |
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| Authors: | Dr Pedro N Leão Hitomi Nakamura Margarida Costa Dr Alban R Pereira Prof Rosário Martins Prof Vitor Vasconcelos Prof William H Gerwick Prof Emily P Balskus |
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| Institution: | 1. Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge MA, 02138 (USA);2. Scripps Institution of Oceanography, University of California, San Diego, La Jolla, CA 92093 (USA);3. Interdisciplinary Centre of Marine and Environmental Research (CIIMAR/CIMAR), University of Porto, Rua dos Bragas, 289, 4050‐123 Porto (Portugal);4. Centre of Health and Environmental Research—CISA, ESTSP, Polytechnic Institute of Porto, Rua Valente Perfeito 322, 4400‐330 Vila Nova de Gaia (Portugal);5. Department of Biology, Faculty of Sciences, University of Porto, Rua do Campo Alegre, 4169‐007 Porto (Portugal);6. Skaggs School of Pharmacy and Pharmaceutical Sciences, University of California, San Diego, La Jolla, CA 92093 (USA) |
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| Abstract: | The isolation of the bartolosides, unprecedented cyanobacterial glycolipids featuring aliphatic chains with chlorine substituents and C‐glycosyl moieties, is reported. Their chlorinated dialkylresorcinol (DAR) core presented a major structural‐elucidation challenge. To overcome this, we discovered the bartoloside (brt) biosynthetic gene cluster and linked it to the natural products through in vitro characterization of the DAR‐forming ketosynthase and aromatase. Bioinformatic analysis also revealed a novel potential halogenase. Knowledge of the bartoloside biosynthesis constrained the DAR core structure by defining key pathway intermediates, ultimately allowing us to determine the full structures of the bartolosides. This work illustrates the power of genomics to enable the use of biosynthetic information for structure elucidation. |
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| Keywords: | biosynthesis cyanobacteria dialkylresorcinol glycolipids structure elucidation |
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