Cross dehydrogenative C–O coupling catalysed by a catenane-coordinated copper(I)

Abstract

Catalytic activity of copper(I) complexes supported by phenanthroline-containing catenane ligands towards a new C(sp3)–O dehydrogenative cross-coupling of phenols and bromodicarbonyls is reported. As the phenanthrolines are interlocked by the strong and flexible mechanical bond in the catenane, the active catalyst with an open copper coordination site can be revealed only transiently and the stable, coordinatively saturated Cu(I) pre-catalyst is quickly regenerated after substrate transformation. Compared with a control Cu(I) complex supported by non-interlocked phenanthrolines, the catenane-supported Cu(I) is highly efficient with a broad substrate scope, and can be applied in gram-scale transformations without a significant loss of the catalytic activity. This work demonstrates the advantages of the catenane ligands that provide a dynamic and responsive copper coordination sphere, highlighting the potential of the mechanical bond as a design element in transition metal catalyst development.