A Regio- and Diastereoselective Stille Coupling/Intramolecular Diels-Alder Cascade for the Generation of Fused Pyridines and Application in the Synthesis of (+)-Lycopladine A and (-)-Lycoposerramine R.

2-Pyrones with a chiral branched allylic silyl ether substituent underwent intramolecular Diels-Alder reactions with remarkably high π-facial- and endo-selectivities. The resulting diastereomerically and enantiomerically pure cycloadducts were transformed into the natural products (+)-lycopladine A and (-)-lycoposerramine R.