A Reappraisal of the Structure of Lyaline as the First Naturally Occurring Nacycline Monoterpene Indole Alkaloid.

Lyaline () is a monoterpene indole alkaloid that was isolated in 1974 from (Rubiaceae) in our laboratory and has not been reported elsewhere since then. Its structure was proposed on the basis of a very limited set of spectroscopic data (viz., H NMR and EIMS) as a structurally bizarre harman-1,4-dihydropyridine derivative. A total synthesis of this proposed structure 30 years later proved this product to be highly unstable, and inconsistencies with the original limited spectroscopic data indicated that the structure proposed for lyaline was incorrect. Having in our laboratory the initial and unique lyaline sample, we decided to reinvestigate it using modern spectroscopic techniques, 47 years after its isolation. Our new spectroscopic data confirmed that the initially assigned harman-1,4-dihydropyridine structure was incorrect, instead establishing lyaline as the first naturally occurring nacycline analogue. This structure revision substantiates a type of chemical reactivity of strictosidine first reported in 1975.