Ruthenium-catalyzed acceptorless dehydrogenative coupling of o-aminobenzyl alcohols with ketones to quinolines in the presence of carbonate salt

Xu, Xiangchao; Ai, Yao; Wang, Rongzhou; Liu, Liping; Yang, Jiazhi; Li, Feng

doi:10.1016/j.jcat.2020.12.016

Cited by 41 publications

(13 citation statements)

References 74 publications

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“…Therefore, this strategy could be used to synthesize regioselectively different substituted quinolines by choice of different 2-amino alcohols, aldehydes, and sulfoxides as substrates. The annulation reaction has been the most important tool for the synthesis of quinolines . We decided to further thoroughly research this newly found reaction with the aim of developing novel and efficient strategies for the regioselective synthesis of quinoline derivatives.…”

Section: Resultsmentioning

confidence: 99%

Unexpected Annulation between 2-Aminobenzyl Alcohols and Benzaldehydes in the Presence of DMSO: Regioselective Synthesis of Substituted Quinolines

Yang

Nie

et al. 2021

J. Org. Chem.

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An unexpected annulation among 2-aminobenzyl alcohols, benzaldehydes, and DMSO to quinolines has been disclosed. For the reported annulation between 2-aminobenzyl alcohols and benzaldehydes, the change of the solvent from toluene to DMSO led to the change of the product from the diheteroatomic cyclic benzoxazines to monoheteroatomic cyclic quinolines. This annulation can be used to synthesize regioselectively different substituted quinolines by the choice of different 2-amino alcohols, aldehydes, and sulfoxides as substrates. Interestingly, introducing substituent groups to the α-position of sulfoxides resulted in the interchange of the positions between benzaldehydes and sulfoxides in the product quinolines. On the basis of the control experiments and literatures, a plausible mechanism for this annulation was proposed.

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Section: Resultsmentioning

confidence: 99%

Unexpected Annulation between 2-Aminobenzyl Alcohols and Benzaldehydes in the Presence of DMSO: Regioselective Synthesis of Substituted Quinolines

Yang

Nie

et al. 2021

J. Org. Chem.

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“…With the increasing requirements for environmental protection, considerable attention has been paid to the development of transition metal-catalyzed acceptorless dehydrogenative reactions with the liberation of hydrogen gas, which represents one of the cleanest and most atom-economical oxidation processes. 8 Very recently, we and other groups also demonstrated the acceptorless dehydrogenative coupling of o -aminobenzyl alcohols with ketones to form quinolines using homogeneous iridium, 9 ruthenium, 10 nickel, 11 manganese 12 and rhenium catalysts. 13 Despite these advances, the practical application of these procedures is highly restricted because the catalysts cannot be recycled.…”

Section: Introductionmentioning

confidence: 98%

A recyclable covalent triazine framework-supported iridium(iii) terpyridine complex for the acceptorless dehydrogenative coupling of o-aminobenzyl alcohols with ketones to form quinolines

Chen

Liu

et al. 2022

Mater. Chem. Front.

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“…Herein, we present the bench-stable bifunctional proton-responsive 2,2′-bibenzimidazole (BiBzImH 2 )-based Ru(II)- para- cymene, C-1 , for the generation of interconvertible coordination modes (imino N → Ru and amido N–Ru) , of C-1 through the hydrogen-bonded interaction between the N–H of the ligand and the CO of the substrate (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Hydrogenation Involving Two Different Proton- and Hydride-Transferring Reagents through Metal–Ligand Cooperation: Mechanism and Scope

2022

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Metal–ligand cooperation (MLC) allows cooperative action between active sites at both the metal and the ligand for transferring hydrogen to the substrate using hydride and proton transfer. Despite their utility in the development of green and sustainable synthetic transformations from a single source, these transfers using two different sources remain limited. Herein, we presented a bench-stable bifunctional 2,2′-bibenzimidazole (BiBzImH2)-based Ru(II)-para-cymene for selective and efficient hydrogenation of unsaturated carbonyl/nitro to saturated carbonyl/nitro using hydride and proton transfer from two different sources (silane for hydride and methanol for proton) via substrate-mediated interconvertible coordination modes (imino N → Ru and amido N–Ru) of the active catalyst. Remarkably, the generation of Ru–H and the presence of N–H of the coordinated BiBzImH2 are important for the generation of interconvertible coordination modes, which in turn is not operative without the N–H. The initial rate kinetics under standard reaction conditions showed a broken positive order in the substrate, first order in the catalyst, and first order in the hydrogen donor (TES). Mechanistic studies, evaluated from spectroscopic, kinetic, Hammett study, kinetic isotope effects (KIEs), and a few other controlled experiments, further reveal that both solvent-mediated proton transfer via the interconvertible coordination mode and hydride transfer between the substrate-coordinated intermediate and Ru–H might be involved in two separate rate-determining steps. The catalyst demonstrated good efficiency, selectivity (>98%), and functional group tolerance and displayed a broad scope with unsaturated ketones and β nitrostyrenes, affording their saturated keto and nitro products with excellent selectivity and emphasizing its potential synthetic utility.

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Ruthenium-catalyzed acceptorless dehydrogenative coupling of o-aminobenzyl alcohols with ketones to quinolines in the presence of carbonate salt

Cited by 41 publications

References 74 publications

Unexpected Annulation between 2-Aminobenzyl Alcohols and Benzaldehydes in the Presence of DMSO: Regioselective Synthesis of Substituted Quinolines

Unexpected Annulation between 2-Aminobenzyl Alcohols and Benzaldehydes in the Presence of DMSO: Regioselective Synthesis of Substituted Quinolines

A recyclable covalent triazine framework-supported iridium(iii) terpyridine complex for the acceptorless dehydrogenative coupling of o-aminobenzyl alcohols with ketones to form quinolines

Hydrogenation Involving Two Different Proton- and Hydride-Transferring Reagents through Metal–Ligand Cooperation: Mechanism and Scope

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