5840-58-4Relevant articles and documents
α-Alkylation of arylacetonitriles with primary alcohols catalyzed by backbone modified N-heterocyclic carbene iridium(i) complexes
Arslan, Burcu,Gülcemal, Süleyman
, p. 1788 - 1796 (2021/02/16)
A series of backbone-modified N-heterocyclic carbene (NHC) complexes of iridium(i) (1d-f) have been synthesized and characterized. The electronic properties of the NHC ligands have been assessed by comparison of the IR carbonyl stretching frequencies of thein situprepared [IrCl(CO)2(NHC)] complexes in CH2Cl2. These new complexes (1d-f), together with previously prepared1a-c, were applied as catalysts for the α-alkylation of arylacetonitriles with an equimolar amount of primary alcohols or 2-aminobenzyl alcohol. The catalytic activities of these complexes could be controlled by modifying the N-substituents and backbone of the NHC ligands. The NHC-IrIcomplex1fbearing 4-methoxybenzyl substituents on the N-atoms and 4-methoxyphenyl groups at the 4,5-positions of imidazole exhibited the highest catalytic activity in the α-alkylation of arylacetonitriles with primary alcohols. Various α-alkylated nitriles and aminoquinolines were obtained in high yields through a borrowing hydrogen pathway by using 0.1 mol%1fand a catalytic amount of KOH (5 mol%) under an air atmosphere within significantly short reaction times.
Copper-catalyzed radical oxidative C(sp3)–H/C(sp3)–H cross-coupling between arylacetonitriles and benzylic compounds
Guo, Fengzhe,Li, Fangshao,Li, Qiang,Tang, Zi-Long,Wu, Xiaofang,Xiao, Jing,Zhong, Ting
, (2020/10/14)
For the first time, a novel copper-catalyzed direct C(sp3)–H/C(sp3)–H cross-coupling of arylacetonitriles with unactivated benzylic compounds was described, allowing various a-benzylated arylacetonitriles to be readily accessible under base-free conditions. Mechanistic investigations suggested that the reaction proceeds through radical process and the C(sp3)–H cleavage of arylacetonitriles probably is the rate-determining step.
Ru(II)-PBTNNXN complex bearing functional 2-(pyridin-2-yl)benzo[d]thiazole ligand catalyzed α-alkylation of nitriles with alcohols
Huang, Shuang,Hong, Xi,Sun, Yong,Cui, He-Zhen,Zhou, Quan,Lin, Yue-Jian,Hou, Xiu-Feng
, (2020/02/13)
Six tridentate NNN ligand precursors derived from 2-(pyridin-2-yl)benzo[d]thiazole(PBT) with different linkers, PBTNNXN (X = NH, NMe, O, S) (1a–1f), have been successfully prepared. The electronic properties of PBTNNXN ligands are well tunable by differing linkers between PBT skeleton and the pyridine ring, and/or by introducing electron-donating/withdrawing groups on the pyridine ring (R = OMe or F). The ligand precursors and representative complexes Ru (PBTNNNHN)Cl2(PPh3) (2a), Ru (PBTNNNMeN)Cl2(PPh3) (2b), and Ru (PBTNNSN)Cl2(PPh3) (2f) have been characterized by NMR spectroscopy, high-resolution mass spectroscopy, and Fourier transform infrared (FT-IR). The molecular structures of 1f, 2a, and 2f have been determined by X-ray diffraction study. The results indicate that PBTNNNHN ligand in the complex presented coplanar with two five-membered chelating rings. It should be noted that 2a featuring a NH group exhibits superior performance compared to those with other linkers (such as NMe, O, or S). A variety of heterocyclic and aromatic nitriles with aromatic and aliphatic alcohols have been explored in α-alkylation for good to excellent yields. Based on kinetic experiments and mechanistic studies, a proposed mechanism was put forward. Ru-H species and benzaldehyde, which was oxidized from benzyl alcohol, were detected in the catalytic cycle.
