On the biosynthetic pathway of papaverine via (S)-reticuline - Theoretical vs. experimental study

Abstract

The electronic structures, optical properties and molecular structures of a series of isoquinoline alkaloids resulting in the formation of papaverine, through a proposed biosynthetic pathway via S(+)-reticuline were elucidated. The mechanism of papaverine synthesis was studied by electronic absorption, diffuse reflectance, fluorescence and CD spectroscopy, as well as ESI and MALDI Orbitrap imaging mass spectrometry. Quantum chemical DFT calculations in the gas phase and solution were performed with a view to study the electronic transitions of the interacting species, corresponding proposed intermediates, and the expected mass spectrometric fragments. The complete study and understanding of the mechanism of the biosynthetic pathway in the poppy plants appears important for the functional oriented drug-design and synthesis of corresponding structurally related alkaloids.