Copper(II)-Catalyzed Aminohalogenation of Alkynyl Carbamates

A useful aminohalogenation reaction for the cyclization of O-alkynyl carbamates under copper catalysis has been developed. N-Halosuccinimides have been used as a halogen source. The intramolecular C-N bond formation occurs selectively affording haloalkylidene substituted heterocycles. Just in the case of alpha,alpha-cyclohexyl-substituted propargyl carbamate, the alkoxyhalogenation pathway was operative. The mechanism for the two alternative reaction pathways was investigated by modeling the corresponding transition states at the DFT level.

Automated summary

A useful aminohalogenation reaction for the cyclization of O-alkynyl carbamates under copper catalysis has been developed in this study. N-Halosuccinimides were used as the halogen source, leading to selective intramolecular C-N bond formation and the generation of haloalkylidene substituted heterocycles. The mechanism for the two alternative reaction pathways was investigated by modeling the corresponding transition states at the DFT level.