Expanding the Scope of Alkynes in C-H Activation: Weak Chelation-Assisted Cobalt-Catalyzed Synthesis of Indole C(4)-Acrylophenone via C-O Bond Cleavage of Propargylic Ethers.

Herein, we report the facile synthesis of indole C(4)-acrylophenone using a C-H bond activation strategy. For this conversion, an unsymmetrical alkyne (phenylethynyl ether) in the presence of cobalt(III)-catalyst works efficiently. In this process, alkyne gets oxidized in the presence of in situ generated water, which is the key step for this method, for which trifluoroethanol is the water source. The pivaloyl directing group chelates effectively to generate the cobaltacycle intermediate, which was detected through high-resolution mass spectrometry (HRMS). Also, the formation of bis(2,2,2-trifluoroethyl) ether has been confirmed and quantified using 19F NMR. In addition, the applicability of obtained indole C(4)-acrylophenone product has been demonstrated by performing the Nazarov cyclization and conjugate addition to the α,ß-unsaturated ketone moiety.

Weak-Chelation Assisted Cobalt-Catalyzed C-H Bond Activation: An Approach Toward Regioselective Ethynylation of N-Aryl γ-Lactam.

The sustainable C-H bond ethynylation of N-aryl γ-lactam has been achieved in a highly regioselective manner. In this protocol, earth-abundant cobalt(III)-catalyst was found to be effective, triggering the C-H metalation using a weakly coordinating lactam group. Herein, the ortho-(sp2)-H ethynylation has been obtained regioselectively. The mechanistic studies reveal the non-involvement of the radical pathway for this conversion. However, the parallel kinetic isotope experiment suggests that the C-H bond activation is involved in the rate-determining step. In addition, the synthetic utility of ethynylated N-aryl γ-lactam has been demonstrated for many useful transformations.