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

Tang, Shan; Wang, Pan; Li, Haoran; Lei, Aiwen · Nat Commun · 2016

basic_science · Level V

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Abstract

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.