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Regioselective Csp 3 –H and Csp 2 –H alkynylation under Ir(III) and Ag(I) catalytic system was developed by judicious choice of readily available and structurally modifiable ketoximes and amides as the key substrates. Key features of this transformation included: 1) For ketoxime substrates, only primary Csp 3 –H at γ position to the nitrogen atom of ketoximes could readily undergo this Csp 3 –H alkynylation under Ir(III) catalysis. Notably, by slight modification of the structure of substrates, alcohols and ketones derived ketoximes could well participate in this transformation. 2) For amide substrates, primary phenylacetamides, which are challenging substrates due to the tautomerization of the distal O ‐coordinating acetamides, could well serve as suitable substrates for the Csp 2 –H alkynylation. Significantly, when using oxidizing amides as the directing groups, α,β‐dehydrogenative C—H alkynylation was achieved. More details are discussed in the article by Shi et al . on page 929—934.