Selective opening of ring C in the morphine skeleton by an unexpected cleavage of the C5-C6 bond in cycloadducts of thebaine and acyl nitroso compounds.
[reaction: see text] Acyl nitroso cycloadducts of the alkaloid thebaine undergo an unexpected cleavage of the C5-C6 bond when treated with 2 equiv of samarium(II) iodide in THF to give novel hexahydrobenzazocine products. A proposed mechanism for the transformation involves rearrangement of the initial radical anion.
Sheldrake
Gary N
GN
School of Chemistry and Chemical Engineering, David Keir Building, Queen's University of Belfast, Belfast BT9 5AG, UK. g.sheldrake@qub.ac.uk
Soissons
Nicolas
N
D000215:Acylation; D008958:Models, Molecular; D008968:Molecular Conformation; D009020:Morphine / Q000737:chemistry*; D009603:Nitroso Compounds / Q000737:chemistry*; D013797:Thebaine / Q000737:chemistry*
D009603:Nitroso Compounds; D013797:Thebaine; D009020:Morphine