Cationic Iridium‐Catalyzed Asymmetric Decarbonylative Aryl Addition of Aromatic Aldehydes to Bicyclic Alkenes. Issue 10 (28th January 2022)

• Record Type: Journal Article
• Authors: Nonami, Reina; Morimoto, Yusei; Kanemoto, Kazuya; Yamamoto, Yasunori; Shirai, Tomohiko
• Is Part Of: Chemistry. Volume 28:Issue 10(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-01-28
• Subjects: asymmetric catalysis -- cationic iridium -- C−H bond activation -- decarbonylation -- decarbonylative arylation; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202104347
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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 (BAr F 4 ) 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. Abstract : 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 ).