(5R)-5-Alkyl-5,6-dihydroindolizines 3a–c having the same high enantiomeric excess (>92 % ) as the corresponding starting olefins (3R)-3-(pyrrol-1-yl)alk-1-enes 1a–c were obtained via a highly regioselective and stereospecific domino hydroformylation/cyclodehydration reaction sequence. The reasons for this configurational stability were also analyzed in the light of the general accepted rhodium catalyzed hydroformylation mechanism.