Ligand-Controlled Copper(I)-Catalyzed Cross-Coupling of Secondary and Primary Alcohols to α-Alkylated Ketones, Pyridines, and Quinolines

Tan, Dali; Li, Hong‐Xi; Zhu, Da-Liang; Li, Haiyan; Young, David J.; Yao, Jianlin; Lang, Jian‐Ping

doi:10.1021/acs.orglett.7b03726

Cited by 128 publications

(59 citation statements)

References 67 publications

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“…[82] Recently, we have been interested in ADC and ATH reactions catalyzed by Cu(I)/Ni(II) N-heterocycle thiolate clusters via ligand-metal cooperative catalysis. [59,72,83] In this work, we have chosen and prepared a family of NH functionalized N^N^N pincer ligands (L1 = 6-(1H-pyrazol-1-yl)-N-(pyridin-2-yl)pyridin-2amine; L2 = 6-(3,5-dimethyl-1H-pyrazol-1-yl)-N-(pyridin-2-yl)pyridin-2-amine; [84] L3 = N-(pyridin-2-yl)-6-(3-(trifluoromethyl)-1Hpyrazol-1-yl)pyridin-2-amine; L4 = 6-(3-phenyl-1H-pyrazol-1-yl)-N-(pyridin-2-yl)pyridin-2-amine) and the methyl-substituted derivative 6-(3,5-dimethyl-1H-pyrazol-1-yl)-N-methyl-N-(pyridin-2yl)pyridin-2-amine (L2 Me ) [84] for the catalytic performance comparison. Reactions of these ligands with equimolar RuCl 3 These Ru(III) and Ru(II) complexes could catalyze ADC reactions of secondary alcohols with 2-aminobenzyl or γ-amino alcohols to give quinolines and pyridines.…”

Section: Introductionmentioning

confidence: 99%

Phosphine Ligand‐Free Ruthenium Complexes as Efficient Catalysts for the Synthesis of Quinolines and Pyridines by Acceptorless Dehydrogenative Coupling Reactions

Guo

et al. 2019

ChemCatChem

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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 [LRuCl3] (L=6‐(3‐R1,5‐R2‐1H‐pyrazol‐1‐yl)‐N‐(pyridin‐2‐yl)pyridin‐2‐amine; 1 a: R1=R2=H (L1); 1 b: R1=R2=Me (L2); 1 c: R1=H, R2=CF3 (L3); 1 d: R1=H, R2=Ph (L4); 1bMe: L=6‐(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)‐N‐methyl‐N‐(pyridin‐2‐yl)pyridin‐2‐amine (L2Me)) were obtained by refluxing RuCl3 ⋅ xH2O with the corresponding ligand in EtOH. Five Ru(II) complexes [LRu(DMSO‐κS)Cl2] (2 a: L=L1; 2 b: L=L2; 2 c: L=L3; 2 d: L=L4; 2bMe: L=L2Me) were formed by reducing the corresponding Ru(III) complex in refluxing EtOH. The latter complexes could also be prepared directly by refluxing Ru(DMSO)4Cl2 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.

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Section: Introductionmentioning

confidence: 99%

Phosphine Ligand‐Free Ruthenium Complexes as Efficient Catalysts for the Synthesis of Quinolines and Pyridines by Acceptorless Dehydrogenative Coupling Reactions

Guo

et al. 2019

ChemCatChem

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“…Tan and colleagues reported a one-pot approach for the synthesis of quinolines (229) using the crosscoupling between the secondary alcohol (227) and 2-aminobenzyl alcohol (228) in presence of hexanuclear Cu(I) cluster of 4,6-dimethylpyrimidine-2-thiolate as bifunctional catalyst (Scheme 85). 113 This methodology was also reported to produce α-alkylated ketone and pyridines through the annulations reaction of secondary alcohol with primary alcohol and γ -amino alcohols respectively. Scheme 87.…”

Section: Various Approaches For the Synthesis Of Quinolines And Theirmentioning

confidence: 93%

A review on transition-metal mediated synthesis of quinolines

2018

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Quinoline is one of the important class of heterocyclic compounds which have gained considerable importance because of its high pharmaceutical efficacy and broad range of biological activities such as anticancer, anti-malarial, anti-microbial and anti-asthmatic. As a consequence, the desire for new versatile and efficient route for the synthesis of quinoline scaffolds remains an active and growing area of interest both in academia and industry. However, developments of transition-metal catalyzed synthetic methods have witnessed a dominant position over the past few years for the synthesis of diverse range of complex heterocyclics containing quinoline scaffolds. This review specifically provides an overview of the literature available on the transitionmetal catalyzed synthetic methodologies for the synthesis of polysubstituted quinoline derivatives.

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“…Metal–ligand cooperation (MLC) plays an important role in catalysis. It can dramatically promote the catalytic activity applied in borrowing hydrogen catalysis using ligands containing functional groups such as NH and OH.…”

Section: Introductionmentioning

confidence: 99%

Ru(II)‐^PBTNN^XN complex bearing functional 2‐(pyridin‐2‐yl)benzo[d]thiazole ligand catalyzed α‐alkylation of nitriles with alcohols

Huang

Hong

Sun

et al. 2020

Applied Organom Chemis

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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.

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Ligand-Controlled Copper(I)-Catalyzed Cross-Coupling of Secondary and Primary Alcohols to α-Alkylated Ketones, Pyridines, and Quinolines

Cited by 128 publications

References 67 publications

Phosphine Ligand‐Free Ruthenium Complexes as Efficient Catalysts for the Synthesis of Quinolines and Pyridines by Acceptorless Dehydrogenative Coupling Reactions

Phosphine Ligand‐Free Ruthenium Complexes as Efficient Catalysts for the Synthesis of Quinolines and Pyridines by Acceptorless Dehydrogenative Coupling Reactions

A review on transition-metal mediated synthesis of quinolines

Ru(II)‐^PBTNN^XN complex bearing functional 2‐(pyridin‐2‐yl)benzo[d]thiazole ligand catalyzed α‐alkylation of nitriles with alcohols

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Ligand-Controlled Copper(I)-Catalyzed Cross-Coupling of Secondary and Primary Alcohols to α-Alkylated Ketones, Pyridines, and Quinolines

Cited by 128 publications

References 67 publications

Phosphine Ligand‐Free Ruthenium Complexes as Efficient Catalysts for the Synthesis of Quinolines and Pyridines by Acceptorless Dehydrogenative Coupling Reactions

Phosphine Ligand‐Free Ruthenium Complexes as Efficient Catalysts for the Synthesis of Quinolines and Pyridines by Acceptorless Dehydrogenative Coupling Reactions

A review on transition-metal mediated synthesis of quinolines

Ru(II)‐PBTNNXN complex bearing functional 2‐(pyridin‐2‐yl)benzo[d]thiazole ligand catalyzed α‐alkylation of nitriles with alcohols

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Ru(II)‐^PBTNN^XN complex bearing functional 2‐(pyridin‐2‐yl)benzo[d]thiazole ligand catalyzed α‐alkylation of nitriles with alcohols