The role of the functional group in double bond migration in allylic systems catalysed by ruthenium hydride complexes

Krompiec, Stanisław; Kuźnik, Nikodem; Krompiec, Michał; Penczek, R.; Mrzigod, J.; Tórz, Artur

doi:10.1016/j.molcata.2006.03.015

Cited by 47 publications

(28 citation statements)

References 85 publications

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“…To this end, we screened a set of structurally related hydridochloro complexes in the isomerization of 1 . Whereas reviews by the Schmidt and Krompiec groups examine the impact of substrate functional groups on isomerization activity,20, 31 systematic comparisons of ligand effects are more limited. As noted above, however, multiple studies suggest that second‐generation [i.e., Ru– N ‐heterocyclic carbene (NHC)] metathesis catalysts trigger more extensive isomerization side‐reactions than their first‐generation analogues 11…”

Section: Methodsmentioning

confidence: 99%

Isomerization During Olefin Metathesis: An Assessment of Potential Catalyst Culprits

2013

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Two ruthenium hydride complexes commonly proposed as agents of unintended isomerization during olefin metathesis are examined for their activity in isomerization of estragole, a representative allylbenzene. Neither proves kinetically competent to account for the levels of isomerization observed during cross‐metathesis of estragole by the second‐generation Grubbs catalyst. A structure–activity analysis of selected ruthenium hydride complexes indicates that higher isomerization activity correlates with a more electrophilic metal center.

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Section: Methodsmentioning

confidence: 99%

Isomerization During Olefin Metathesis: An Assessment of Potential Catalyst Culprits

2013

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“…The influence of solvent (Table S1) and temperature (Table S2) on the catalytic isomerization provided further clues to the synergetic effect between the Ru−H complex and non‐redox metals. Trace conversion was observed but no isomerization product was detected in CH 3 CN and DMSO, which was probably because of the coordinating properties of these solvent molecules . A 16.3 % conversion was observed if 1,4‐dioxane and N , N ‐dimethylethanamide were used, whereas alcoholic solvents such as methanol, ethanol, isopropanol, and tert ‐butanol led to a better performance.…”

Section: Resultsmentioning

confidence: 91%

A General Strategy for Open‐Flask Alkene Isomerization by Ruthenium Hydride Complexes with Non‐Redox Metal Salts

Chen

et al. 2017

ChemCatChem

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A homogenous metal hydride (M−H) catalyst for isomerization normally requires rigorous air‐free techniques. Here, we demonstrate a highly efficient protocol in which simple non‐redox metal ions as Lewis acids can promote olefin isomerization dramatically with a commercially available RuH2(CO)(PPh3)3 complex in an open‐flask system. Isomerization can be accomplished within a short time, and a satisfactory selectivity for different types of unsaturated compounds can be obtained. Meanwhile, an excellent turnover number up to 17208 was achieved under air, and open‐flask gram‐scale experiments further demonstrated the efficiency of the RuH2(CO)(PPh3)3/non‐redox‐metals system. We used FTIR spectroscopy, GC–MS, NMR spectroscopy and kinetics studies to evidence that in the sluggish RuH2(CO)(PPh3)3 catalyst, bloated PPh3 ligands cause steric hindrance for the coordination of the free alkene. Alternatively, the addition of non‐redox metal ions could induce the dissociation of the PPh3 ligand to offer unoccupied coordination sites for the alkene and to form the Mg‐bridged adduct OC−Ru−H2−Mg2+ as the highly active species, which benefited the isomerization significantly through the metal hydride addition–elimination pathway. Finally, this strategy was demonstrated as an impactful approach for hydride catalysts of other transition metals such as Os.

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“…We observed that [ReBr(CO) 3 (THF)] 2 left in the reaction system increased the Diels-Alder [4+2] reaction yield [28,29]. It is worth noting that there was no rhenium catalyst system deactivation (through the formation of stable complexes with 2,2 0 -bithiophene-5-yl) -in many cases those catalytic systems are inactive due to strong coordination of substrate by a transition metal catalytic center [39]. There are number of stable neutral and cationic transition metals (Cr, Ru, Ir, Rh, Mn, Re, Ti, Cu, Fe, etc.)…”

Section: Synthesis Of Multi-substituted Benzene and Naphthalene Derivmentioning

confidence: 89%

Synthesis and photophysical properties of novel multisubstituted benzene and naphthalene derivatives with high 2D-π-conjugation

et al. 2015

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The role of the functional group in double bond migration in allylic systems catalysed by ruthenium hydride complexes

Cited by 47 publications

References 85 publications

Isomerization During Olefin Metathesis: An Assessment of Potential Catalyst Culprits

Isomerization During Olefin Metathesis: An Assessment of Potential Catalyst Culprits

A General Strategy for Open‐Flask Alkene Isomerization by Ruthenium Hydride Complexes with Non‐Redox Metal Salts

Synthesis and photophysical properties of novel multisubstituted benzene and naphthalene derivatives with high 2D-π-conjugation

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