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While gold‐mediated synergistic catalytic processes involving transmetalations with other metals are well understood, AuI/AuIII cycles in these reactions are rarely reported. Herein a gold‐catalyzed direct alkynylation of cyclopropenes is enabled by two operating catalytic cycles, an oxidative catalytic cycle involving an alkynyl AuIII complex formed by oxidative addition and one involving a silver‐mediated...
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