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

Reina Nonami; Yusei Morimoto; Kazuya Kanemoto; Yasunori Yamamoto; Tomohiko Shirai

doi:10.1002/chem.202104347

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

Chemistry. 2022 Feb 21;28(10):e202104347. doi: 10.1002/chem.202104347. Epub 2022 Jan 28.

Authors

Reina Nonami¹, Yusei Morimoto¹, Kazuya Kanemoto², Yasunori Yamamoto³, Tomohiko Shirai¹

Affiliations

¹ Department of Social Design Engineering National Institute of Technology, Kochi College, 200-1 Monobe Otsu, Nankoku, Kochi, 783-8508, Japan.
² Department of Applied Chemistry Institute of Science and Engineering, Chuo University, Kasuga 1-3-27, Bunkyo-ku, Tokyo, 112-8551, Japan.
³ Division of Applied Chemistry Graduate School of Engineering, Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan.

PMID: 35019188
DOI: 10.1002/chem.202104347

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.

Keywords: C−H bond activation; asymmetric catalysis; cationic iridium; decarbonylation; decarbonylative arylation.

Grants and funding

JP19K15575/Japan Society for the Promotion of Science