One-pot reductive amination of carbonyl compounds with ammonia via ‘hydrogen borrowing’ using hydrido- and bis-ammine P,O(Me)-ruthenacycles

Noh, Ji‐Hyang; Naganagowda, Gadada; Singleton, Eric; Meijboom, Reinout

doi:10.1016/j.jorganchem.2016.10.038

Cited by 5 publications

(1 citation statement)

References 40 publications

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“…[17][18][19][20] More recently, Ru catalystsi nt ransfer hydrogenation have been used for this transformation by Thiel et al and Zhu. [21,22] Selectivity for primary amines using Ru complexes has also been shown by Meijboom et al [23] Herein we describe results from recent studies in which we used catalysts based on Triphos ruthenium complexes. Initial catalytic studies in which aT riphos ruthenium complexw as used were performedb yE lsevier et al for the hydrogenation of dimethyl oxalate.…”

Section: Introductionsupporting

confidence: 56%

Hydrogenation and Reductive Amination of Aldehydes using Triphos Ruthenium Catalysts

2018

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An air‐stable and readily accessible ruthenium dihydride complex catalyses aldehyde hydrogenation under neutral conditions. A high activity has been shown in a number of examples, and solvent‐free conditions are also applicable, which favours industrial‐scale applications. The catalyst has also been demonstrated to be active at low catalyst loadings for the reductive amination of aldehydes under mildly acidic conditions. A number of examples of chemoselectivity challenges are also presented in which the catalyst does not reduce carbon−halogen groups, alkene or ketone functionality. The advantage of using the pre‐formed complex, Triphos‐Ru(CO)H2 (1), over in situ formed catalysts from Triphos and Ru(acac)3 (acac=acetylacetonate) is also shown in terms of both chemoselectivity and activity, in particular this can be seen if low reaction temperatures are used.

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Section: Introductionsupporting

confidence: 56%

Hydrogenation and Reductive Amination of Aldehydes using Triphos Ruthenium Catalysts

2018

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Unexpected Vulnerability of DPEphos to C−O Activation in the Presence of Nucleophilic Metal Hydrides

Cybulski

Beattie

Macgregor

et al. 2020

Chemistry A European J

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C−O bond activation of DPEphos occurs upon mild heating in the presence of [Ru(NHC)2(PPh3)2H2] (NHC=N‐heterocyclic carbene) to form phosphinophenolate products. When NHC=IEt2Me2, C−O activation is accompanied by C−N activation of an NHC ligand to yield a coordinated N‐phosphino‐functionalised carbene. DFT calculations define a nucleophilic mechanism in which a hydride ligand attacks the aryl carbon of the DPEphos C−O bond. This is promoted by the strongly donating NHC ligands which render a trans dihydride intermediate featuring highly nucleophilic hydride ligands accessible. C−O bond activation also occurs upon heating cis‐[Ru(DPEphos)2H2]. DFT calculations suggest this reaction is promoted by the steric encumbrance associated with two bulky DPEphos ligands. Our observations that facile degradation of the DPEphos ligand via C−O bond activation is possible under relatively mild reaction conditions has potential ramifications for the use of this ligand in high‐temperature catalysis.

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Structural, Electrochemical and Catalytic Elucidation of Cyclooctadiene Ru(II)‐Nitrile Complexes of the Type [RuCl₂(cod)(NCR)₂]

Malan

2022

ChemistrySelect

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The facile synthesis of a range of eleven cyclooctadiene Ru(II) complexes of the type [RuCl 2 (cod)(NCR) 2 ] featuring different nitrile ligands using two synthetic routes is reported. The solidstate characterization (SCXRD) of twelve complexes is also described. Complex instability in solution led to spontaneous dimerization to yield a dimeric complex. Using these complexes, varied catalytic activity was observed in six different transformation reactions, of which the transfer hydrogenation of ketones was the highest (yields of 99 % after 30 minutes, TOF = 156 h À 1 ). The electrochemical (CV), DFT, and catalytic properties of the complexes evaluated showed that while the majority of the characteristics of the complexes are comparable, three complexes stood out with the lowest catalytic activity (16 % and lower), the highest (most positive) formal redox potentials for Ru II /Ru III (E 0 ' of up to + 1.4 V), as well as exhibiting some of the smallest energy gaps (as small as 1.21 eV) in the series.

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One-pot reductive amination of carbonyl compounds with ammonia via ‘hydrogen borrowing’ using hydrido- and bis-ammine P,O(Me)-ruthenacycles

Cited by 5 publications

References 40 publications

Hydrogenation and Reductive Amination of Aldehydes using Triphos Ruthenium Catalysts

Hydrogenation and Reductive Amination of Aldehydes using Triphos Ruthenium Catalysts

Unexpected Vulnerability of DPEphos to C−O Activation in the Presence of Nucleophilic Metal Hydrides

Structural, Electrochemical and Catalytic Elucidation of Cyclooctadiene Ru(II)‐Nitrile Complexes of the Type [RuCl₂(cod)(NCR)₂]

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One-pot reductive amination of carbonyl compounds with ammonia via ‘hydrogen borrowing’ using hydrido- and bis-ammine P,O(Me)-ruthenacycles

Cited by 5 publications

References 40 publications

Hydrogenation and Reductive Amination of Aldehydes using Triphos Ruthenium Catalysts

Hydrogenation and Reductive Amination of Aldehydes using Triphos Ruthenium Catalysts

Unexpected Vulnerability of DPEphos to C−O Activation in the Presence of Nucleophilic Metal Hydrides

Structural, Electrochemical and Catalytic Elucidation of Cyclooctadiene Ru(II)‐Nitrile Complexes of the Type [RuCl2(cod)(NCR)2]

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Product

Resources

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Structural, Electrochemical and Catalytic Elucidation of Cyclooctadiene Ru(II)‐Nitrile Complexes of the Type [RuCl₂(cod)(NCR)₂]