Insights into mechanism and selectivity in ruthenium(<scp>ii</scp>)-catalysed <i>ortho</i>-arylation reactions directed by Lewis basic groups

McIntyre, J.M.; Mayoral-Soler, Irene; Salvador, Pedro; Poater, Albert; Nelson, David J.

doi:10.1039/c8cy00592c

Cited by 26 publications

(22 citation statements)

References 59 publications

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“…In contrast to the values computed by Nelson et al, 16 in this study the relative value of B′ to A is over 10 kcal mol −1 more stable. 35 However, relative barrier heights and product stability are similar in size.…”

Section: Neutral Vs Cationic C-h Activationcontrasting

confidence: 99%

“…More recently, Nelson et al published a comparison between cationic arene and arene-free Ru catalysed C-H activation of 2-phenylpyiridine. 16 Again energy values for these pathways appear higher than experimentally anticipated. However, no additional solvent molecules were included in the computational model, and the focus of the study was the viability of the subsequent oxidative addition of phenyl halides.…”

Section: Introductionmentioning

confidence: 69%

“…Finally, as mentioned in the introduction, the role of the arene co-ligand and whether it remains coordinated throughout the reaction process led Nelson et al to suggest a new potential C-H activation pathway starting at B′, 16 [Ru(a-H) (OAc) 2 ] ΔG MeCN = +0.8 kcal mol −1 . This pathway has no arene, but two κ 2 coordinated acetate ligands.…”

Section: Neutral Vs Cationic C-h Activationmentioning

confidence: 99%

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A computational study on the identity of the active catalyst structure for Ru(ii) carboxylate assisted C–H activation in acetonitrile

2019

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Section: Neutral Vs Cationic C-h Activationcontrasting

confidence: 99%

Section: Introductionmentioning

confidence: 69%

Section: Neutral Vs Cationic C-h Activationmentioning

confidence: 99%

See 1 more Smart Citation

A computational study on the identity of the active catalyst structure for Ru(ii) carboxylate assisted C–H activation in acetonitrile

2019

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“…These reactions on ruthenium-catalysed C-H bond functionalization have been presented in numerous research papers and review articles by several groups [15,16,25,26,[38][39][40]. Furthermore, the mechanistic study of ruthenium-catalysed C-H bond functionalization was recently described by the research group of Lan [41] in the context of arylation, alkylation and alkenylation,and by Nelson and co-workers on selective ortho-arylation directed by Lewis basic groups [42]. However, new reactions and methodologies ofC-H bond functionalization with ruthenium-based catalysts are being discovered.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in C–H Bond Functionalization with Ruthenium-Based Catalysts

Singh

2019

Catalysts

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The past decades have witnessed rapid development in organic synthesis via catalysis, particularly the reactions through C–H bond functionalization. Transition metals such as Pd, Rh and Ru constitute a crucial catalyst in these C–H bond functionalization reactions. This process is highly attractive not only because it saves reaction time and reduces waste,but also, more importantly, it allows the reaction to be performed in a highly region specific manner. Indeed, several organic compounds could be readily accessed via C–H bond functionalization with transition metals. In the recent past, tremendous progress has been made on C–H bond functionalization via ruthenium catalysis, including less expensive but more stable ruthenium(II) catalysts. The ruthenium-catalysed C–H bond functionalization, viz. arylation, alkenylation, annulation, oxygenation, and halogenation involving C–C, C–O, C–N, and C–X bond forming reactions, has been described and presented in numerous reviews. This review discusses the recent development of C–H bond functionalization with various ruthenium-based catalysts. The first section of the review presents arylation reactions covering arylation directed by N–Heteroaryl groups, oxidative arylation, dehydrative arylation and arylation involving decarboxylative and sp3-C–H bond functionalization. Subsequently, the ruthenium-catalysed alkenylation, alkylation, allylation including oxidative alkenylation and meta-selective C–H bond alkylation has been presented. Finally, the oxidative annulation of various arenes with alkynes involving C–H/O–H or C–H/N–H bond cleavage reactions has been discussed.

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“…. Thus, it can easily be linked to different functional groups and inspire various economic processes …”

Section: Introductionmentioning

confidence: 99%

One‐pot stepwise reductive amination reaction by N‐coordinate sulfonamido‐functionalized Ru(II) complexes in water

Kayacı

Dayan

Özdemir

et al. 2018

Applied Organom Chemis

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New complexes of formula [RuCl(p-cymene)(L)] (7-12) were prepared with [RuCl 2 (p-cymene)] 2 and pre-synthesized N-arenesulfonly-o-phenylenediamines(1-6) and characterized using 1 H NMR, 13 C NMR, Fourier transform infrared and UV-visible spectroscopic techniques, and single-crystal X-ray diffraction analysis was performed for one complex (8). Complexes 7-12 were investigated in the reduced imine synthesis reaction (in the presence of HCOONa/HCOOH). The best turnover frequency values were found to be 100 h −1 for 1 and 99 h −1 for 6 in the transfer hydrogenative reductive amination reaction of 4-methoxyaniline and 3,4,5-trimethoxybenzaldehyde. The most important feature of this reaction is that it is an environmental friendly procedure because of being conducted in an aqueous environment. That no organic solvent is used allows one to say that this reaction represents green chemistry.

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Insights into mechanism and selectivity in ruthenium(ii)-catalysed ortho-arylation reactions directed by Lewis basic groups

Abstract: We report a detailed study of the mechanism and selectivity of ruthenium-catalysed C–H arylation reactions directed by Lewis basic heterocycles.

Cited by 26 publications

References 59 publications

A computational study on the identity of the active catalyst structure for Ru(ii) carboxylate assisted C–H activation in acetonitrile

A computational study on the identity of the active catalyst structure for Ru(ii) carboxylate assisted C–H activation in acetonitrile

Recent Advances in C–H Bond Functionalization with Ruthenium-Based Catalysts

One‐pot stepwise reductive amination reaction by N‐coordinate sulfonamido‐functionalized Ru(II) complexes in water

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