Lupin alkaloids Part IV. The influence of some structural factors on the conformational equilibrium in bis-quinolizidine systems

Abstract

13C NMR and IR spectra of minor alkaloids of Lupinus albus such as multiflorine ( I), 13α-hydroxymultiflorine ( IV) and their monoperchlorates, 13α-hydroxy-5-dehydromultiflorine ( V) and 5-dehydromultiflorine ( VI) were taken. I and IV in CDCl 3, their monoperchlorates in CD 3CN and V in CD 3OD solution occur in conformational equilibrium. The share of the conformation with a boat ring C in I is about 74%, in IV 67%, in I · HClO 4 20%, in IV·HClO 43% and in V 3%. The change in conformational preference results mainly from a decreasing destabilization of the conformation with a chair ring C caused by an increase in the distance between the interacting hydrogen atom pairs 5α–17α, 8β–12β, 12β–17β and 14β–17β, due to protonation induced lengthening of the N (16)-C α bonds. VI and most of the molecules of V remain in solution in conformation with a chair ring C. This conformation in V and VI is less destabilized than in I and IV because of a lower steric hindrance for the chair ring C, as a consequence of the planarity of ring A and a part of fragment B and because of the absence of the 5α–17α interaction.