Rhodium(III)-Catalyzed Synthesis of Skipped Enynes via C(sp3)-H Alkynylation of Terminal Alkenes.

The Rh(III)-catalyzed allylic C-H alkynylation of non-activated terminal alkenes leads to linear 1,4-enynes at room-temperature. The catalytic system tolerates a wide range of functional groups without competing functionalization at other positions. Similarly, the vinylic C-H alkynylation of α,β- and β,γ- unsaturated amides gives conjugated Z-1,3-enynes and E-enediynes.