The first total synthesis and structural validation of phosdiecin A was accomplished in 13 steps (LLS) through asymmetric iridium-catalyzed alcohol-mediated carbonyl reductive coupling. The present route is the shortest among >30 total and formal syntheses of fostriecin family members.

The total synthesis and structural revision of (+)-cryptoconcatone H are described. Guided by computational studies for the final structure assignment, the stereogenic centers at the tetrahydropyran moiety of (+)-cryptoconcatone H were assembled through catalytic asymmetric methodologies: Krische allylation, cross-metathesis reaction, and THP formation via Pd(II)-catalyzed cyclization. Finally, a Krische allylation reaction established the last stereocenter, and the lactone moiety was formed by ring-closing metathesis.

The structural, biological, and pharmacological profiles of phosphorylated secondary metabolites is presented. An overview of the phosphorylation methodologies employed in their total syntheses is also included.