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.