Rearrangement of a variety of 3-(2-methyleneaziridin-1-yl) propyl radicals, generated using Bu3SnH/AIBN by homolytic cleavage of phenylselenide substituted 2-methyleneaziridines, produces 3-methylenepiperidines in yields ranging from 58 to 68%. By combining this radical rearrangement with an additional 5-exo-trig cyclisation, this method provides an octahydroindolizine with moderate levels of diastereocontrol (dr= 4: 1). This ...