Total syntheses and stereochemical reassignments of mollenines A and B

Abstract Total syntheses of prenylated pyrrolidinoindoline alkaloids, (−)-mollenines A [(−)- 1 ′] and B ( 2 ′), were accomplished via three- and four-step sequences including a bioinspired indole prenylation reaction followed by dioxomorpholine ring formation. Then, the stereochemistry of mollenines A and B was reassigned to 3 S ,6 S ,14 S ,16 S by analysis of spectroscopic data and chemical syntheses with different approaches along with the comparison of calculated and experimental ECD spectra. In addition, a thermodynamically controlled epimerization reaction on the dioxomorpholine ring was observed in our synthesis.