Absolute configuration of neostenine

Heavy atoms bromine and iodine were incorporated into the neostenine (1) skeleton through reductive cleavage of the lactone ring, followed by acylation with 4-bromobenzoyl chloride, and salt formation with methyl iodide, respectively. The absolute configuration of the seven chiral centers C1, C9, C9a, C10, C11, C1 and C13 in 1 were assigned as S, S, R, R, R, R, and S, respectively, based on the Flack parameters in X-ray structure refinement, and results from the two heavy atom derivatives are consistent with each other. As many Stemona alkaloids share the same lactone and pyrrolo[1,2-α]azepine nucleus as those in 1, the facile method reported in this paper can be applied for the determination of absolute configurations of similar alkaloids.