A series of planar chiral 1,1A-P,N-2A-substituted ferrocene ligands 9-12 and 16, prepared with diastereopurity > 99+1, have been used to examine the role of planar chirality, and significant effects on enantioselectivity as well as the control of absolute configuration in palladium-catalyzed allylic alkylation as a model reaction were observed.

The enantioselective total synthesis and structure revision of spirodihydrobenzofuranlactam 1 and of its regioisomer 25 are presented. Optically pure (+)-Wieland-Miescher ketone was utilized to construct the AB bicyclic core in 10 steps. Introduction of the resorcylate D-ring unit was achieved by use of our tert-butyl ester metalation sequence. Subsequent stereoselective spirocyclization to form the C-ring was followed by regioselective ring cyanation and lactam formation to produce the pentacyclic structure 1 and its regioisomer 25.