Mechanistic studies on the CAN-mediated intramolecular cyclization of δ-aryl-β-dicarbonyl compounds.
The synthesis of 2-tetralones through the cyclization of δ-aryl-β-dicarbonyl substrates by using CAN is described. Appropriately functionalized aromatic substrates undergo intramolecular cyclizations generating 2-tetralone derivatives in moderate to good yields. DFT computational studies indicate that successful formation of 2-tetralones from δ-aryl-β-dicarbonyl radicals is dependent on the stability of the subsequent cyclohexadienyl radical intermediates. Furthermore, DFT computational studies were used to rationalize the observed site selectivity in the 2-tetralone products.
Department of Chemistry, Lehigh University, Bethlehem, PA 18015, USA.
Brian M
BM
Casey
Dhandapani V
DV
Sadasivam
Robert A
RA
Flowers Ii
CAN oxidation; free radical; radical arylations; tetralones; β-dicarbonyls