Synthesis, Structural Elucidation, And Biochemical Analysis of Immunoactive Glucuronosyl Diacylglycerides of Mycobacteria and Corynebacteria
Benjamin Cao, Xingqiang Chen, Yoshiki Yamaryo-Botte, Mark B Richardson, Kirstee L Martin, George N Khairallah, Thusita WT Rupasinghe, Roisin M O'Flaherty, Richard AJ O'Hair, Julie E Ralton, Paul K Crellin, Ross L Coppel, Malcolm J McConville, Spencer J Williams
JOURNAL OF ORGANIC CHEMISTRY | AMER CHEMICAL SOC | Published : 2013
Glucuronosyl diacylglycerides (GlcAGroAc2) are functionally important glycolipids and membrane anchors for cell wall lipoglycans in the Corynebacteria. Here we describe the complete synthesis of distinct acyl-isoforms of GlcAGroAc2 bearing both acylation patterns of (R)-tuberculostearic acid (C19:0) and palmitic acid (C16:0) and their mass spectral characterization. Collision-induced fragmentation mass spectrometry identified characteristic fragment ions that were used to develop "rules" allowing the assignment of the acylation pattern as C19:0 (sn-1), C16:0 (sn-2) in the natural product from Mycobacterium smegmatis, and the structural assignment of related C18:1 (sn-1), C16:0 (sn-2) GlcAGro..View full abstract
We thank Prof. Mark Rizzacasa for helpful advice. Financial support from the Australian Research Council and Australian National Health and Medical Research Council is gratefully acknowledged. MJ.M. is an NHMRC Principal Research Fellow.