An unprecedented catalytic protocol for the asymmetric decarbonylative transformation: The cover art depicts how the asymmetric reaction of the Ir/S−Me‐BIPAM complex takes precedence over the decarbonylation. The picture of the balance shows that the competing decarbonylation side reaction will not happen, as well as highlighting the asymmetry. More information can be found in the Research Article by T. Shirai et al. (DOI: 10.1002/chem.202104347).

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 CÀ C bonds through the formation of an arylÀ iridium intermediate. The decarbonylative aryl addition to bicyclic alkenes was fluidly performed without a stoichio-metric arylÀ metal reagent, such as aryl boronic acid, with a cationic iridium complex generated in situ from Ir(cod) 2 (BAr F 4 ) and the sulfur-linked bis(phosphoramidite) ligand ((R,R)-SÀ MeÀ BIPAM). This reaction has broad functional group compatibility, and no waste is generated, except carbon monoxide.

Invited for the cover of this issue are Tomohiko Shirai and co‐workers at the National Institute of Technology Kochi College and their collaborators at Chuo and Hokkaido Universities. The image depicts how asymmetric decarbonylative C−C bond formation by the Ir/S‐Me‐BIPAM complex takes precedence over aldehyde decarbonylation. Read the full text of the article at 10.1002/chem.202104347.