Copper complexes with N-alkylated NS2-macrocyclic ligands:: Synthesis, characterization, and capabilities as aziridination precatalysts

The syntheses of two new ligands containing macrocyclic [10]-aneNS(2) (1-aza-4,8-dithiacyclodecane) units are reported, including the N-methylated analogue (L-Me) and a dinucleating version that separates two [10]-aneNS(2) groups with a m-xylyl spacer (L-2). Copper complexes with these new ligands as well as previously reported related complexes have been found to mediate the aziridination of olefins. Thus, isolated copper complexes containing the ethylnaphthyl-appended [10]-aneNS(2) macrocyclic ligand (L-nap), including [(LCu)-Cu-nap]PF6 (1) and [(LCu)-Cu-nap(CH3CN)]PF6 (2), the Cu(I) complex [(LCu)-Cu-Me(CH3CN)]PF6 (3), and the Cu(II) complex (LCuBr2)-Cu-Me (4), were compared in their ability to function as aziridination precatalysts. In addition, the aziridination capabilities were probed for complexes generated in situ from copper(I) ion sources and L-2, 1,4,7-triazacyclononane, 1,4,7-trithiacyclononane, or 1,4,7-trimethyl-1,4,7-triazacyclononane. The synthesis and characterization of the new complexes 3 and 4 are reported, including X-ray crystal structures. The aziridination reaction using precatalyst 3 was examined for its tolerance to different functional groups near the olefin as well as to the use of other nitrogen group sources and reaction conditions.