DescriptionThe complete structure of Psymberin was determined with the application of the Universal NMR database approach. A formal synthesis of psymberin was completed with the application of spirodiepoxides. An assembly of a dihydroisocumarin ring was accomplished from a complex aldehyde and an anion derived from a pentasubstituted arene. A new condition to couple an aldehyde and an amide was achieved to reach a carbinolamide moiety. This condition was applied for the synthesis of analogs and hybrid structures. In a separate study, a metal and a ligand were investigated to promote the coupling between thioacids and azides.