Selective construction of fused heterocycles by an iridium-catalyzed reductive three-component annulation reaction

Catalytic conversion of ubiquitously distributed but less reactive N-heteroarenes into functional products remains to date a challenge. Here, through an initial pretreatment of N-heteroarenes with alkyl bromide, we describe a syn-selective construction of functional fused heterocycles via iridium catalyzed reductive annulation of N-heteroarenium salts with formaldehyde and cyclic 1,3-diketones or 4-hydroxycoumarins, proceeding with broad substrate scope, good functional group compatibility, readily available feedstocks, and high step and atom efficiency.