Multimetallic catalysed radical oxidative C(sp(3))–H/C(sp)–H cross-coupling between unactivated alkanes and terminal alkynes

Radical involved transformations are now considered as extremely important processes in modern organic synthetic chemistry. According to the demand by atom-economic and sustainable chemistry, direct C(sp(3))–H functionalization through radical oxidative coupling represents an appealing strategy for C–C bond formations. However, the selectivity control of reactive radical intermediates is still a great challenge in these transformations. Here we show a selective radical oxidative C(sp(3))–H/C(sp)–H cross-coupling of unactivated alkanes with terminal alkynes by using a combined Cu/Ni/Ag catalytic system. It provides a new way to access substituted alkynes from readily available materials. Preliminary mechanistic studies suggest that this reaction proceeds through a radical process and the C(sp(3))–H bond cleavage is the rate-limiting step. This study may have significant implications for controlling selective C–C bond formation of reactive radical intermediates by using multimetallic catalytic systems.