Reported herein is a general and efficient method to construct 2,3,6-trisubstituted piperidines in a substituent-independent fashion. From the high enantiopurity organometallic scaffold (-)-Tp(CO)(2)[(eta-2,3,4)-(1S,2S)-1-benzyl-oxycarbonyl-5-oxo-5,6-clihydro-2H-pyridin-2-yl)molybdenum (Tp = hydrido-trispyrazolylborato), a variety of TpMo(CO)(2)-based 2,3,6-trifunctionalized complexes of the (eta-3,4,5-dihydropyridinyl) ligand were easily obtained in 5 steps through a sequence of highly regio- and stereospecific metal-influenced transformations (15 examples). From the 2,3,6-trifunctionalized molybdenum complexes, either 2,6-cis-3-trans or 2,3,6-cis systems were selectively obtained through the choice of an appropriate stereodivergent demetalation protocol. The potential of this strategy in synthetic chemistry was demonstrated by the short total synthesis of four natural and one non-natural alkaloids: indolizidines (+/-)-209I and (+/-)-8-epi-219F in the racemic series, and enantiocontrolled syntheses of (-)-indolizidine 251N, (-)-quinolizidine 251AA, and ()-dehydroindolizidine 233E.