Computationally Assisted Structural Revision of Flavoalkaloids with a Seven-Membered Ring: Aquiledine, Isoaquiledine, and Cheliensisine.

Aquiledine and cheliensisine are flavoalkaloids isolated from Aquilegia ecalcarata and Goniothalamus cheliensis, respectively. Different structures have been proposed for these flavoalkaloids; however, their 1H and 13C NMR spectroscopic data were virtually identical. In this study, the structures of aquiledine and cheliensisine were revised on the basis of the DFT calculation of NMR data including DP4+ and J-DP4 analysis, as well as specific rotations. Similarly, the structure of isoaquiledine, a regioisomer of aquiledine, was also revised. A biosynthetic pathway of these flavoalkaloids is proposed.