Well-Defined Phosphine-Free Iron-Catalyzed N-Ethylation and N-Methylation of Amines with Ethanol and Methanol

• DOI: 10.1021/acs.orglett.8b02080
• Publication Date: 2018-09-20T18:15:27Z
• Authors: Alexis Lator; Sylvain Gaillard; Albert Poater; Jean-Luc Renaud
• Keywords: [CHIM.ORGA]Chemical Sciences/Organic chemistry; [CHIM.CATA]Chemical Sciences/Catalysis; [CHIM.MATE]Chemical Sciences/Material chemistry; 01 natural sciences; 0104 chemical sciences

An iron(0) complex bearing a cyclopentadienone ligand catalyzed N-methylation and N-ethylation of aryl and aliphatic amines with methanol or ethanol in mild and basic conditions through a hydrogen autotransfer borrowing process is reported. A broad range of aromatic and aliphatic amines underwent mono- or dimethylation in high yields. DFT calculations suggest molecular hydrogen acts not only as a reducing agent but also as an additive to displace thermodynamic equilibria.