Cobalt-Catalyzed C8-Dienylation of Quinoline-N-Oxides

An efficient Cp*Co-III-catalyzed C8-dienylation of quinoline-N-oxides was achieved by employing allenes bearing leaving groups at the alpha-position as the dienylating agents. The reaction proceeds by Co-III-catalyzed C-H activation of quinoline-N-oxides and regioselective migratory insertion of the allene followed by a beta-oxy elimination, leading to overall dienylation. Site-selective C-H activation was achieved with excellent selectivity under mild reaction conditions, and 30 mol % of a NaF additive was found to be crucial for the efficient dienylation. The methodology features high stereoselectivity, mild reaction conditions, and good functional-group tolerance. C8-alkenylation of quinoline-N-oxides was achieved in the case of allenes devoid of leaving groups as coupling partners. Furthermore, gram-scale preparation and preliminary mechanistic experiments were carried out to gain insights into the reaction mechanism.