N-centered radicals in self-terminating radical cyclizations: experimental and computational studies.
Intermolecular addition of photochemically generated N-centered aminium and amidyl radicals 13a-d and 16a,b, respectively, to the cyclic alkyne 1 initiates a radical translocation/cyclization cascade, followed by an oxidative termination step that eventually leads to formation of the bicyclic ketones 7a and 8a. Computational studies were performed to gain insight into the mechanism of these reactions, which are an interesting modification of the recently discovered concept of self-terminating radical cyclizations.
Wille
Uta
U
School of Chemistry/BIO21 Molecular Science and Biotechnology Institute, The University of Melbourne, 30 Flemington Road, Parkville, Victoria 3010, Australia. uwille@unimelb.edu.au
Heuger
Gerold
G
Jargstorff
Christian
C
D000588:Amines / Q000737:chemistry*; D002849:Chromatography, Gas; D003500:Cyclization; D009682:Magnetic Resonance Spectroscopy
D000588:Amines