Heterogeneous Olefin Aziridination Reactions Catalyzed by Polymer‐Bound Tris(triazolyl)methane Copper Complexes

Abstract

Efficient olefin aziridination has been achieved with a tris (triazolyl)methane copper catalyst supported onto polystyrene. Aryl, alkyl and methoxycarbonyl-substituted olefins are con-verted into N-tosylaziridines in good to high yields. The solid catalyst is readily separated by filtration and recycled, allowing its reuse with no significant loss of the catalytic activity.

Non-innocent Role of the Halide Ligand in the Copper-Catalyzed Olefin Aziridination Reaction

“…Complexes (TTM)CuCl 10 ( 1 ) and [(TTM)Cu(NCMe)]PF 6 11 ( 2 ) (TTM = 4,4′,4″-(methoxymethanetriyl)tris(1-benzyl-1H-1,2,3-triazole)) were first employed in the probe reaction of styrene and PhI = NTs as nitrene precursor ( Scheme 2 , see the Experimental Section for details). The yields into the desired aziridine varied from 71% for 1 to quantitative with 2 , as a first distinction between these catalysts.…”

“…The residue was dissolved in DCM (4 mL), and the DCM was again removed to obtain complexes 1 and 2 as white solids, which were dried under vacuum. 10,11 General Olefin Aziridination Experiment. The [TTMCu]X (X = PF 6 , Cl) complex (0.01 mmol) was dissolved in deoxygenated DCM (6 mL) before olefin (1 mmol) was added.…”

“…MeCN was removed at reduced pressure to obtain a colorless oil. The residue was dissolved in DCM (4 mL), and the DCM was again removed to obtain complexes 1 and 2 as white solids, which were dried under vacuum. , …”