214492-76-9Relevant academic research and scientific papers
Biosynthesis of angular furanocoumarins: Mechanism and stereochemistry of the oxidative dealkylation of columbianetin to angelicin in Heracleum mantegazzianum (Apiaceae)
Stanjek, Volker,Boland, Wilhelm
, p. 1596 - 1607 (1998)
Deuterium-labelled 5-fluorocolumbianetin 13 was synthesized as a metabolic probe to examine the stereochemical course of the bioconversion of (+)-columbianetin (12) into the angular furocoumarin angelicin (5). In leaves of Heracleum mantegazzianum, oxidative dealkylation of the specifically deuterated fluorocolumbianetin 13 proceeded by syn-elimination of a D-atom, from C(9), and the vicinal 1-hydroxy-1-methylethyl substituent, yielding 5- fluoroangelicin (23). This matches the stereochemical course of the related reaction converting (+)-marmesin (10) into the linear furocoumarin psoralen (1). Key steps in the synthesis of 5-fluorocolumbianetin (13) were the copper-catalysed alkynylation/cyclization of 5-fluoro-8-iodoumbelliferone (15) followed by a transfer hydrogenation, which established the cis- orientation of the D-Atom and the 1-hydroxy-1-methylethyl substituent.
