Abstract
A series of phosphine-free Ru(III)/Ru(II) complexes of NH functionalized N ˄ N ˄ N pincer ligands exhibit excellent activity for acceptorless dehydrogenative coupling (ADC) of secondary alcohols with 2-aminobenzyl or γ-amino alcohols to quinolines and pyridines. Ru(III) complexes [LRuCl 3 ] (L=6-(3-R 1 ,5-R 2 -1H-pyrazol-1-yl)-N-(pyridin-2-yl)pyridin-2-amine; 1 a: R 1 =R 2 =H (L1); 1 b: R 1 =R 2 =Me (L2); 1 c: R 1 =H, R 2 =CF 3 (L3); 1 d: R 1 =H, R 2 =Ph (L4); 1b Me : L=6-(3,5-dimethyl-1H-pyrazol-1-yl)-N-methyl-N-(pyridin-2-yl)pyridin-2-amine (L2 Me )) were obtained by refluxing RuCl 3 ⋅ xH 2 O with the corresponding ligand in EtOH. Five Ru(II) complexes [LRu(DMSO-κS)Cl 2 ] (2 a: L=L1; 2 b: L=L2; 2 c: L=L3; 2 d: L=L4; 2b Me : L=L2 Me ) were formed by reducing the corresponding Ru(III) complex in refluxing EtOH. The latter complexes could also be prepared directly by refluxing Ru(DMSO) 4 Cl 2 with the corresponding ligand in EtOH. These Ru(III) and Ru(II) complexes, especially 1 b/2 b, exhibited high catalytic efficiency and broad functional group tolerance in ADC reactions of secondary alcohols with 2-aminobenzyl or γ-amino alcohols to quinolines and pyridines. A detail mechanistic study indicated the Ru(III) complex was reduced into the Ru(II) species, which is the active catalytic center for ADC via a Ru−H/N−H bifunctional outer-sphere mechanism. This protocol provides a reliable, atom-economical and environmentally benign procedure for C−N and C−C bond formation.
Original language | English |
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Pages (from-to) | 2500-2510 |
Number of pages | 11 |
Journal | ChemCatChem |
Volume | 11 |
Issue number | 10 |
Early online date | 10 Apr 2019 |
DOIs | |
Publication status | Published - 20 May 2019 |