We have devised both a contiguous and a stepwise strategy for the synthesis of the pyridylaminomethane-based class of phosphonoalkylphosphinates (PAPs) that form via the intermediacy of the phosphonoethoxyaminomethane XIa. The PAPs result from condensation of picolines and phosphonoacetals in high chemoselective yield. Following reduction of aminopyridine IIIb, the unprecedented Pt (0)-catalyzed epimerization of the ...