Structure and biosynthesis of desmamides A-C, lipoglycopeptides from the endophytic cyanobacterium Desmonostoc muscorum LEGE 12446

Certain cyanobacteria of the secondary metabolite-rich order Nostocales can establish permanent symbioses with a large number of cycads, by accumulating in their coralloid roots and shifting their metabolism to dinitrogen fixa-tion. Here, we report the discovery of two novel lipoglycopeptides, desmamides A (1) and B (2), together with their aglycone desmamide C (3), from the nostocalean cyanobacterium Desmonostoc muscorum LEGE 12446 isolated from a cycad (Cycas revoluta) coralloid root. The chemical structures of the compounds were elucidated using a combination of 1D and 2D Nuclear Magnetic Resonance (NMR) spectroscopy and Mass Spectrometry (MS). The desmamides are decapeptides, featuring O-glycosylation of tyrosine (in 1 and 2) and an unusual 3,5-dihydroxy-2-methyldecanoic acid residue. The biosynthesis of the desmamides was studied by substrate feeding experiments and bioinformatics. We describe herein the dsm biosynthetic gene cluster (BGC) and propose it to be associated with desmamide production. The discovery of this class of very abundant (>1.5% d.w.) bacterial lipoglycopeptides paves the way for exploration of their potential role in root endosymbiosis.