Mild and Efficient Synthesis of Diverse Organo‐AuI‐L Complexes in Green Solvents

An exceptionally mild and efficient method was developed for the preparation of (hetero)aryl‐AuI‐L complexes using ethanol or water as the reaction medium at room temperature and Ar‐B(triol)K boronates as the transmetalation partner. The reaction does not need an exogeneous base or other additives, and quantitative yields can be achieved through a simple filtration as the only required purification method, which obviates considerable waste associated with alternative workup methods. A broad reaction scope was demonstrated with respect to both the L and (hetero)aryl ligands on product Au complexes. Despite the polar reaction medium, large polycyclic aromatic hydrocarbon units can be incorporated on the Au complexes in very good to excellent yields. The approach was demonstrated for the chemoselective manipulation of orthogonally protected aryl boronates to afford a new class of N‐heterocyclic carbene‐Au‐aryl complexes. A mechanistic rationale was proposed. Triols and triturations! High‐yield synthesis of diverse aryl‐AuI complexes is achieved under mild conditions in green solvents (ethanol or water) by harnessing the unique properties of aryl‐B(triol)K boronates. The method permits transmetalation from aryl‐B(triol)K boronates while preserving aryl‐B(pin) boronates on the substrate. Pure products are obtained through a simple filtration.