Synthesis and reactions of polymer-bound Ph3P=C=C=O: a quick route to tenuazonic acid and other optically pure 5-substituted tetramates

Polystyrene-bound cumulated ylide Ph3PCCO was prepared on a large scale in two steps. It reacts with Grignard compounds, amines and alcohols to give immobilized acyl, amide and ester ylides, respectively. Their Wittig reactions lead to alkenes free of phosphane oxide. Optically pure 5-substituted tetramates were obtained from reactions of resin-bound Ph3PCCO with alpha-ammonium esters in one step. The mycotoxin (-)-tenuazonic acid was accordingly prepared in just three steps.