A highly effective synthesis of haloalkylidene-substituted heterocycles by copper(II)-catalyzed cyclization of alkynyl ureas and secondary amides has been developed. The reaction, which involves a catalytic amount of CuCl2 and a stoichiometric amount of N-halosuccinimide, occurs selectively through an alkoxyhalogenation process. Alternatively, alkoxychlorination and alkoxybromination reactions can be performed working solely with stoichiometric CuCl2 and CuBr2, respectively.

Two complementary Pd-catalyzed protocols enabling the γ-selective intermolecular allylic amination of but-3-enoic acid derivatives are reported. These transformations can be successfully achieved via either a direct Pd(II)-catalyzed protocol or by way of a one-pot Pd(II)/Pd(0)-catalyzed sequence, depending on the nature of the nitrogen nucleophile used

3-Aza-5-alkenols undergo selective 7-endo-trig cyclization when treated with a catalytic Pd(II) species, CuCl2 and ArSnBu3 giving 7-aryl-substituted oxazepanes. The intramolecular alkoxylation occurs with formation of a seven-membered ring only when associated with an arylating step. Otherwise, 6-exo-trig reactions, providing morpholine derivatives, were observed.

Copper(II)-Catalyzed Alkoxyhalogenation of Alkynyl Ureas and Amides as a Route to Haloalkylidene-Substituted Heterocycles. -(GAZZOLA, S.; BECCALLI, E. M.; BORELLI, T.; CASTELLANO, C.; CHIACCHIO, M. A.; DIAMANTE, D.; BROGGINI*, G.; J. Org. Chem. 80 (2015) 14, 7226-7234, http://dx.doi.org/10.1021/acs.joc.5b01227 ; Dip. Sci. Alta Tecnol., Univ. Insubria, I-22100 Como, Italy; Eng.) -T. Stabingis 51-136