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Cyclobutadiene Rhodium Complexes as Catalysts for the Synthesis of Amides from Electron‐rich Arenes, Tosyl Azide and CO
Author(s) -
Shvydkiy Nikita V.,
Petrushina Tatia.,
Perekalin Dmitry S.
Publication year - 2021
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.202100344
Subject(s) - cyclobutadiene , chemistry , nitrene , rhodium , azide , tosyl , cycloaddition , medicinal chemistry , photochemistry , catalysis , carbon monoxide , metallacycle , organic chemistry , molecule , x ray crystallography , physics , diffraction , optics
Cyclobutadiene rhodium complexes [(C 4 R 4 )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 TsN 3 with CO via cycloaddition and formation of RhCON 3 metallacycle, which is more favorable than the commonly assumed formation of nitrene intermediate.