Calixanthomycin A: Asymmetric Total Synthesis and Structural Determination.

We report the first asymmetric total synthesis and structural determination of calixanthomycin A. Taking advantage of a modular strategy, a concise approach was developed to assemble the hexacyclic skeleton with both enantiomers of the lactone A ring. Stereoselective glycosylation coupled the angular hexacyclic framework with a monosaccharide fragment to produce calixanthomycin A and its stereoisomers. This enable us to determine and assign the absolute configuration of C-25 (25S) and monosaccharide (derivative of l-glucose).