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ementation of transannular reactions or reaction cascades that can lead to rapid and substantial increases in molecular complexity. The examples summarized herein showcase such possibilities, with special emphasis on tranannular gold catalysis and the emerging ruthenium-catalyzed trans-hydrometalation chemistry for the selective functionalization of alkynes.The mechanochemical reaction kinetics of sulfur with copper to form a metastable copper sulfide phase at room temperature is investigated in ultrahigh vacuum by modifying the properties of the co