Ethynylbenziodazolones (EBZ) as Electrophilic Alkynylation Reagents for the Highly Enantioselective Copper‐Catalyzed Oxyalkynylation of Diazo Compounds

Ethynylbenziodoxol(on)e (EBX) cyclic hypervalent iodine reagents are now established reagents for the alkynylation of radicals and nucleophiles, yet they present limited possibilities for further structure and reactivity modification. Herein, the first synthesis is reported for the corresponding ethynylbenziodazolone (EBZ) reagents, in which the oxygen atom in the iodoheterocycle is replaced by a nitrogen atom. The substituent on the nitrogen enables further fine‐tuning of the reagent structure and reactivity. EBZ reagents are obtained easily from the corresponding benzamides by using a one‐step procedure, and display reactivity comparable to that of EBX reagents. In particular, they are applied in an asymmetric copper‐catalyzed oxyalkynylation of diazo compounds, which proceeds in high yield and enantioselectivity for a broad range of substituents on the diazo compounds and the alkyne. Enantioselective reagents: Ethynylbenziodazolone (EBZ) cyclic hypervalent iodine reagents are synthesized for the first time, and display similar structure and reactivity to the established ethynylbenziodoxolone (EBX) reagents. They are used in the oxyalkynylation of diazo compounds to access imidate derivatives in high yield and enantioselectivity for a broad scope of diazo compounds and alkynes (see figure).