Daphnillonins A and B: Alkaloids Representing Two Unknown Carbon Skeletons from Daphniphyllum longeracemosum.

Two highly rearranged daphniphyllum alkaloids, daphnillonins A (1) and B (2), were isolated from Daphniphyllum longeracemosum and structurally characterized by a combination of diverse methods, including the calculation of electronic circular dichroism. Compound 1 possesses an unprecedented carbon architecture with a very unique 8-methyl-6-azabicyclo[3.2.1]octane moiety, and compound 2 represents a new carbon skeleton with an uncommon 7/6/5/7/5/5-fused ring system. The biosynthetic pathways for the two alkaloids were proposed with the concurrent major alkaloids as the precursors.