Cyclobutadiene Rhodium Complexes as Catalysts for the Synthesis of Amides from Electron‐rich Arenes, Tosyl Azide and CO. Issue 12 (18th May 2021)

• Record Type: Journal Article
• Authors: Shvydkiy, Nikita V.; Petrushina, Tatiana N.; Perekalin, Dmitry S.
• Is Part Of: ChemCatChem. Volume 13:Issue 12(2021)
• Page Start: 2873
• Page End: 2878
• Publication Date: 2021-05-18
• Subjects: Carbonyl ligands -- Cyclobutadiene -- Density functional calculations -- Homogeneous catalysis -- Rhodium.; Catalysis -- Periodicals; 541.39505
• DOI: 10.1002/cctc.202100344
• Languages: English
• ISSNs: 1867-3880

Abstract

Abstract: Cyclobutadiene rhodium complexes [(C4 R4 )RhX]2 (R=Et, Ph; X=I, Cl) at 0.5 mol % loading catalyze the formation of aromatic amides from various indoles, tosyl azide, and carbon monoxide (1 atm). The reaction gives good yields of the target products (typically 60–85 %) and tolerates both donor and moderately acceptor substituents in the indoles (alkyl, OMe, Hal, COOMe, but not CN). The DFT calculations at the PBE/3ζ level revealed a new plausible mechanism for the reaction of TsN3 with CO via cycloaddition and formation of RhCON3 metallacycle, which is more favorable than the commonly assumed formation of nitrene intermediate. Abstract : Catalysts of a new type : Readily available cyclobutadiene rhodium complexes catalyze the synthesis of amides directly from donor arenes, CO, and tosyl azide. The scope of substrates for such transformations can be rationalized in terms of nucleophilic and electrophilic properties of reagents.