Nickel-Catalyzed Heteroarenes Cross Coupling via Tandem C–H/C–O Activation

Inert aryl methyl ethers as coupling components via C–O activation have been established with a Ni catalyst for C–H activation of heteroarene. The key to simultaneous C–H/C–O bond activation is the use of sterically demanding o-tolylMgBr. The protocol is effective for a wide scope of substrates including naphthyl methyl ethers, anisoles, and a variety of other heteroarene derivatives. Detailed mechanistic studies indicated that the C–O cleavage is assisted via synergistic effect of nickel and Grignard reagent in this C–H/C–O reaction, which is supported by DFT calculation. At this stage, single-electron transfer can be ruled out as a main operative process for this tandem strategy.