Boron-to-gold transmetalation: a useful platform for gold(iii) cyclometalation.

Boron-to-gold transmetalation represents a fundamental step in the generation of organogold species, yet its potential for constructing complex architectures remains underexplored. Here, we harness this elementary step to devise a general platform for the synthesis of mono- and bis-cyclometalated gold(iii) complexes. The approach enables access to structurally diverse (N^C)- and (N^C^C)-frameworks, as well as a single example of a (C^N^C)-framework, under remarkably mild, neutral conditions devoid of toxic reagents. Mechanistically, an intriguing B-N dative interaction confirmed by X-ray diffraction analysis underpins the transmetalation process, establishing a new paradigm for the modular construction of cyclometalated gold(iii) species.