Neat total synthesis of six monoterpenic alkaloids of the actinidine series

A concise enantiopure synthesis of six monoterpenic alkaloids of the actinidine series possessing a cyclopentac]pyridine skeleton, (+)-deoxyrhexifoline (4), (+)-boschniakinic acid (5), (+)-boschniakine (6), (−)-plantagonine (7), (−)-indicaine (8) and (−)-tecostidine (9) is reported starting with the chiral precursor 3-bromo-5-((4R)-phenyloxazolin-2-yl)pyridine (10). It involves a C-4 regioselective connection of a butene appendice and an intramolecular 5-exo-trig Heck annulation sequence followed by hydrogenation of the exocyclic alkene. Mixture of (3R)- and (3S)-7-((4R)-phenyloxazolin-2-yl)cyclopentac]pyridines was separated by HPLC before being transformed into enantiopure natural products (4-9) by modification of the oxazoline group.