Details

Autor(en) / Beteiligte

• Tomita, Eiki
• Kojima, Masahiro
• Nagashima, Yuki
• Tanaka, Ken
• Sugiyama, Haruki
• Segawa, Yasutomo
• Furukawa, Atsushi
• Maenaka, Katsumi
• Maeda, Satoshi
• Yoshino, Tatsuhiko
• Matsunaga, Shigeki

Titel

An Electron‐Deficient CpE Iridium(III) Catalyst: Synthesis, Characterization, and Application to Ether‐Directed C−H Amidation

Ist Teil von

• Angewandte Chemie International Edition, 2023-05, Vol.62 (21), p.e202301259-n/a

Auflage

International ed. in English

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2023

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The synthesis, characterization, and catalytic performance of an iridium(III) catalyst with an electron‐deficient cyclopentadienyl ligand ([CpEIrI2]2) are reported. The [CpEIrI2]2 catalyst was synthesized by complexation of a precursor of the CpE ligand with [Ir(cod)OAc]2, followed by oxidation, desilylation, and removal of the COD ligand. The electron‐deficient [CpEIrI2]2 catalyst enabled C−H amidation reactions assisted by a weakly coordinating ether directing group. Experimental mechanistic studies and DFT calculations suggested that the high catalytic performance of [CpEIrI2]2 is due to its electron‐deficient nature, which accelerates both C−H activation and IrV‐nitrenoid formation. A highly electron‐deficient cyclopentadienyl iridium(III) complex was developed ([CpEIrI2]2). This complex effectively catalyzed weakly coordinating ether‐directed C−H amidation reactions under mild reaction conditions. Mechanistic experiments and DFT calculations indicated that the high catalytic activity of the [CpEIrI2]2 complex is attributed to its highly electron‐deficient nature.