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Biosynthesis‐Assisted Structural Elucidation of the Bartolosides, Chlorinated Aromatic Glycolipids from Cyanobacteria
Author(s) -
Leão Pedro N.,
Nakamura Hitomi,
Costa Margarida,
Pereira Alban R.,
Martins Rosário,
Vasconcelos Vitor,
Gerwick William H.,
Balskus Emily P.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201503186
Subject(s) - biosynthesis , chemistry , gene cluster , glycolipid , glycosyl , cyanobacteria , biochemistry , chemical space , natural product , stereochemistry , combinatorial chemistry , computational biology , drug discovery , gene , biology , bacteria , genetics
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.