Iridium‐Catalyzed Enantioselective Formal <i>meta</i> ‐Allenylation of Pyridines

Site-selective functionalization of pyridines is an important yet challenging transformation. Temporary dearomatization of pyridines through redox-neutral cycloaddition has recently emerged as a reliable and attractive strategy for meta-functionalization of pyridines. Despite the amenability of the resulting bench-stable cycloadduct, oxazinopyridine, to a variety of electrophilic and radical-based reagents, its enantioselective functionalization remains unexplored. Herein, we present the first enantioselective meta-functionalization of pyridines through the intermediacy of oxazinopyridines. This highly enantioselective formal meta-allenylation of pyridines is achieved by treating the easily accessible oxazinopyridines with racemic allenylic alcohol under the combination of a catalytic amount of an Ir(I)/(P, olefin) complex and Lewis acidic Sc(OTf)₃ followed by acid-mediated rearomatization. With oxazinopyridines derived from unsubstituted or suitably substituted pyridines, iterative 3,5-difunctionalization is possible, which also allows for the stereodivergent synthesis of all four stereoisomers of 3,5-bis-allenylic pyridines.