Dearomatization Reactions of N-Heterocycles Mediated by Group 3 Complexes
Kevin L. Miller, Bryan N. Williams, Diego Benítez, Colin T. Carver, Kevin R. Ogilby, Ekaterina Tkatchouk, William A. Goddard III, Paula L. Diaconescu
Abstract
Group 3 (Sc, Y, Lu, La) benzyl complexes supported by a ferrocene diamide ligand are reactive toward aromatic N-heterocycles by mediating their coupling and, in a few cases, the cleavage of their C−N bonds. When these complexes reacted with 2,2′-bipyridine or isoquinoline, they facilitated the alkyl migration of the benzyl ligand onto the pyridine ring, a process accompanied by the dearomatization of the N-heterocycle. The products of the alkyl-transfer reactions act as hydrogen donors in the presence of aromatic N-heterocycles, ketones, and azobenzene. Experimental and computational studies suggest that the hydrogen transfer takes place through a concerted mechanism. An interesting disproportionation reaction of the dearomatized, alkyl-substituted isoquinoline complexes is also reported.
Group Members
Miller, K. L., Williams, B. N., Benítez, D., Carver, C. T., Ogilby, K. R., Tkatchouk, E., III, W. A. G., & Diaconescu, P. L. (2010). Dearomatization Reactions of N-Heterocycles Mediated by Group 3 Complexes. *J. Am. Chem. Soc.*, *132*(1), 342-355. https://doi.org/10.1021/ja908489p