Cationic Iridium‐Catalyzed Asymmetric Decarbonylative Aryl Addition of Aromatic Aldehydes to Bicyclic Alkenes

We report an unprecedented catalytic protocol for the enantioselective decarbonylative transformation of aryl aldehydes. In this process, the decarbonylation of aldehydes catalyzed by chiral iridium complexes enabled the formation of asymmetric C−C bonds through the formation of an aryl−iridium intermediate. The decarbonylative aryl addition to bicyclic alkenes was fluidly performed without a stoichiometric aryl−metal reagent, such as aryl boronic acid, with a cationic iridium complex generated in situ from Ir(cod)2(BArF4) and the sulfur‐linked bis(phosphoramidite) ligand ((R,R)‐S−Me−BIPAM). This reaction has broad functional group compatibility, and no waste is generated, except carbon monoxide. Building bridges: We have developed an unprecedented asymmetric decarbonylative aryl addition of an aromatic aldehyde to bicyclic alkenes, catalyzed by chiral cationic iridium. This process provides efficient access to a wide variety of enantioenriched bridged bicyclic systems from aromatic aldehydes in high yields and with excellent enantioselectivities (up to 90 % yield and up to 99 % ee).