Free-radical selective functionalization of 1,4-naphthoquinones by perfluorodiacyl peroxides

Cover image Tetrahedron

Author(s): Maurizio Sansotera, Cristian Gambarotti, Antonino Famulari, Alberto Baggioli, Raffaella Soave, Francesco Venturini, Stefano V. Meille, Ivan Wlassics, Walter Navarrini

Source: Tetrahedron

Volume: 70 Pages: 5298-5309

Published: Aug (2014)

DOI: 10.1016/j.tet.2014.05.024



Perfluoroalkyl radicals, generated by thermal decomposition of perfluorodiacyl peroxides, react selectively with quinone rings of 1,4-naphthoquinones. In the presence of a non-conjugated alkene such as 1-hexene, perfluoroalkyl radicals add to the double bonds of the olefin forming a radical adduct, which selectively adds to the naphthoquinone ring. Several perfluorodiacyl peroxides have been synthesized and used for the direct and alkene-mediated functionalization of naphthoquinones. Geometrical parameters and electron density topology of all perfluorodiacyl peroxides have been calculated by the density functional formalism and quantum theory of atoms in molecules to attempt a rationalization of the experimental reactivity.