Rapid access to the core skeleton of the [3+2]-type dimeric pyrrole-imidazole alkaloids by triplet ketone-mediated C-H functionalization

The ability of triplet ketones to abstract a hydrogen atom from hydrocarbons is reminiscent of that of the high-spin metal-oxo complexes in C-H oxidation enzymes. In practice, the reactivity of triplet ketones is easier to control and applicable to promoting a wider range of reactions. We demonstrate herein the synthetic utility of triplet ketone-mediated C-addition of methanol to cyclopentenone derivatives with an expedient synthesis of the core skeleton of the [3 + 2]-type dimeric pyrrole imidazole alkaloids. Remarkably, this photochemical C-H functionalization reaction is highly regioselective and can tolerate a good range of functional groups. (C) 2017 Elsevier Ltd. All rights reserved.