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

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 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.

Enantioselective catalytic radical decarbonylative azidation and cyanation of aldehydes

“…However, state-of-the-art methods rely heavily on precious metal catalysts (Rh, Ir, Ru, Pd, etc.) and high temperatures to avoid catalyst deactivation ( 16 ). The conventional 2e pathway has presented a huge challenge to asymmetric decarbonylative functionalization.…”

Ru(II)-Catalyzed Decarbonylative Alkylation and Annulations of Benzaldehydes with Iodonium Ylides under Chelation Assistance

“…More recently, the Rao group reported the Rh­(I)-catalyzed decarbonylative addition and heck-type reactions of salicylaldehydes with activated alkenes . Shirai and co-worker realized the asymmetric decarbonylative aryl addition of benzaldehydes to bicyclic alkenes under Ir­(I) catalysis using a protected amino group as the directing group (Scheme c) . Despite these notable achievements, the reported procedures are largely restricted to the use of expensive catalysts (Rh and Ir), and the decarbonylation and annulation reaction of salicylaldehydes and 2-aminobenzaldehydes under inexpensive Ru­(II) catalyst has not been realized yet.…”