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

Under basic conditions aryl halides can undergo S(RN)1 reactions, BHAS reactions and benzyne formations. Appropriate complex substrates afford an opportunity to study inherent selectivities. S(RN)1 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. 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license.