C-C bond-forming reactions of ground-state aryl halides under reductive activation

Emery, Katie J. and Tuttle, Tell and Kennedy, Alan R. and Murphy, John A. (2016) C-C bond-forming reactions of ground-state aryl halides under reductive activation. Tetrahedron, 72 (48). pp. 7875-7887. ISSN 0040-4020 (https://doi.org/10.1016/j.tet.2016.05.083)

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Under basic conditions aryl halides can undergo SRN1 reactions, BHAS reactions and benzyne formations. Appropriate complex substrates afford an opportunity to study inherent selectivities. SRN1 reactions are usually favoured under photoactivated conditions, but this paper reports their success using ground-state and transition metal-free conditions. In benzene, the enolate salt 12, derived by deprotonation of diketopiperazine 11, behaves as an electron donor, and assists the initiation of the reactions, but in DMSO, it is not required. The outcomes are compared and contrasted with a recent photochemical study on similar substrates. A particular difference is the prevalence of hydride shuttle reactions under relatively mild thermal conditions.