Manganese(I)‐Catalyzed Regio‐ and Stereoselective 1,2‐Diheteroarylation of Allenes: Combination of C−H Activation and Smiles Rearrangement

Heteroarenes are important structural motif in functional molecules. Reported herein is a Mn(I)-catalyzed 1,2-diheteroarylation of allenes via a C-H activation/Smiles rearrangement cascade. The reaction occurred under additive-free or even solvent-free conditions which allowed the creation of two C-C and one C-N bonds in a single operation. A series of structurally diverse bicyclic or tricyclic compounds bearing an exocyclic double bond were constructed in good to excellent efficiency. The decarboxylative ring-opening of the products led to the facile synthesis of vicinal biheteroaryls. Synthetic applications were demonstrated and preliminary mechanistic studies were conducted.