Ni-catalyzed benzylic β-C(sp<sup>3</sup>)-H bond activation of formamides.

Wang, Rong-Hua; Xu, Wei-Wei; Wu, Hongli; Li, Yue; Li, Jiang-Fei; Zhang, Tao; Huang, Genping; Ye, Mengchun · Nat Commun · 2022

basic_science · Level V

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Abstract

The development of transition metal-catalyzed β-C-H bond activation via highly-strained 4-membered metallacycles has been a formidable task. So far, only scarce examples have been reported to undergo β-C-H bond activation via 4-membered metallacycles, and all of them rely on precious metals. In contrast, earth-abundant and inexpensive 3d transition metal-catalyzed β-C-H bond activation via 4-membered metallacycles still remains an elusive challenge. Herein, we report a phosphine oxide-ligated Ni-Al bimetallic catalyst to activate secondary benzylic C(sp<sup>3</sup>)-H bonds of formamides via 4-membered nickelacycles, providing a series of α,β-unsaturated γ-lactams in up to 97% yield.