| Popis: |
As a continuing effort of expanding the scope of catalyst regeneration in the presence of environmentally benign reducing agents, one-pot sequential azide–alkyne [3+2] cycloaddition and atom transfer radical addition (ATRA) reactions were performed via in situ reduction of copper(II) by ascorbic acid. The formation of functionalized triazoles was achieved utilizing a ligand-free catalytic system for the cycloaddition between tripropargylamine and vinylbenzyl azide and subsequent addition of tris(2-pyridyl)methylamine (TPMA) ligand in the ATRA step. With this strategy, reactions with carbon tetrachloride and carbon tetrabromide proceeded efficiently providing the desired triazoles in nearly quantitative yields (>90 %) using 10 mol % of copper. Sequential azide–alkyne [3+2] cycloaddition and ATRA reactions were also extended to less active alkyl halides such as methyl trichloroacetate, methyl dichloroacetate and dichloroacetonitrile. The corresponding products were obtained in modest yields (50–80 %). The presented methodology enables efficient synthesis of functionalized polytriazoles, which could have a potential use as chelating agents for a variety of transition metals. |
