84553-32-2Relevant articles and documents
Control over C-O and C-C bond formation: ruthenium catalyzed regiospecific addition of carboxylic acid to alkyne and stereoselective dimerization of alkyne
Tripathy, Jyotsna,Bhattacharjee, Manish
supporting information; experimental part, p. 4863 - 4865 (2009/11/30)
A cationic ruthenium(II) complex, [Ru(PPh3)2(CH3CN)3Cl][BPh4] (1), has been found to be an effective catalyst for stereoselective dimerization of alkynes in the presence of a base, and for regiospecific addition of carboxylic acids to alkynes in presence of the Lewis acid, BF3·Et2O.
Immobilized ruthenium complexes bearing N,O-bidentate ligands
Drǎgu?an, Valerian,Verpoort, Francis
, p. 905 - 915 (2008/09/20)
Immobilization of a family of arene and benzylidene N,O-bidentate ruthenium complexes by covalently anchoring the homogeneous complexes on MCM-41 is described. Successful applications of these immobilized catalytic systems in enol-ester synthesis, Kharasch addition, ring-closing metathesis (RCM), ring-opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP) are illustrated. Important advantages of these heterogeneous catalyst systems in comparison with their homogeneous counterparts are also highlighted.
Synthesis of enol esters and dimerization of terminal alkynes catalyzed by neutral and cationic vinylidene ruthenium complexes
Opstal, Tom,Verpoort, Francis
, p. 314 - 320 (2007/10/03)
In the current study Ru(II) vinylidene complexes of the general type: Cl2Ru{=C=C(H)R}(PR′3)L (R = Ph, SiMe3, R′ = Ph, Cyclohexyl (Cy) and L = phosphine or N-heterocyclic carbene) are synthesized and tested for the addition of carboxylic acids to terminal alkynes. A careful choice of the catalytic system, substrate and carboxylic acid gives access to alk-1-en-2-yl esters, alk-1-en-1-yl esters or enyne dimerization products. Furthermore, an extension was made to synthesize an analogous 14-electron species by treating one of the complexes with AgBF4 and its influence on the catalytic activity and selectivity are investigated.
A new heterogeneous hybrid ruthenium catalyst being an eco-friendly option for the production of polymers and organic intermediates
De Clercq, Bob,Lefebvre, Frederic,Verpoort, Francis
, p. 1201 - 1208 (2007/10/03)
We succeeded in synthesising and characterising a new heterogeneous hybrid ruthenium catalyst that exhibits excellent stability, reusability and leaching characteristics. The host-guest interaction is studied by XRD, XRF, ICP/MS, BET, FT-Raman and solid state NMR analysis. Moreover, we tested this catalytic system in ring-closing metathesis (RCM), ring-opening metathesis polymerization (ROMP), Kharasch addition, atom transfer radical polymerization (ATRP) and vinylation reactions. The results obtained from these tests show that for ROMP, RCM, Kharasch addition and vinylation reactions the heterogeneous catalyst possesses important advantages in comparison with its homogeneous analogue.
Selective dimerisation and addition of carboxylic acids to terminal alkynes, catalysed by thermolysed Grubbs' catalyst: A novel synthesis of enynes and vinyl esters
Melis, Karen,Opstal, Tom,Verpoort, Francis
, p. 3779 - 3784 (2007/10/03)
The transformation of triple bonds of terminal alkynes was carried out at 110 °C in the presence of the thermolysed RuII-alkylidene [Cl2(PCy3)2Ru=CHPh]. The transformation of phenylacetylene is strongly pKa-dependent, the preference switching from vinylation to dimerisation at increasing pKa values. Aliphatic alkynes only give rise to vinylation adducts, with a regioselectivity for Markovnikov addition. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
Ruthenium-catalyzed selective anti-Markovnikov trans addition of carboxylic acids and tail-to-tail dimerization of terminal alkynes
Melis, Karen,Samulkiewicz, Pawel,Rynkowski, Jacek,Verpoort, Francis
, p. 2713 - 2716 (2007/10/03)
Carboxylic acids react with terminal alkynes in the presence of a catalytic amount of RuClx(p-cymene)(triazol-5-ylidene) to selective generate Z-alk-1-en-1-yl esters. The anti-Markovnikov and trans addition on the terminal alkyne gives access t
Atom transfer radical addition and enol-ester synthesis catalyzed by Ru-vinylidene complexes
Opstal, Tom,Verpoort, Francis
, p. 9259 - 9263 (2007/10/03)
Ru-vinylidene complexes, Cl2Ru{=C=C(H)tBut}(PCy3)(L) (L=PCy3 or N-heterocyclic carbenes) reveal themselves as a versatile catalyst for the atom transfer radical addition (ATRA) of polyhalogenated alkanes to olefins, such as methylmethacrylate, styrene and 1-octene. Furthermore, these systems are excellent catalysts for the nucleophilic addition of carboxylic acids to terminal alkynes and yielded exclusively alk-1-en-2-yl esters. These complexes can also be transformed to their cationic counterparts by treating the neutral complexes with AgBF4 and their catalytic potential in ATRA and vinylation reaction are investigated.
Ruthenium indenylidene and vinylidene complexes bearing Schiff bases: Potential catalysts in enol-ester synthesis
Opstal, Tom,Verpoort, Francis
, p. 935 - 941 (2007/10/03)
In an extension of our previous investigations on the ruthenium(II) Schiff-base chemistry, complexes 1, 2, 3a-b and 4a-b were synthesized and tested as catalyst for the nucleophilic addition of carboxylic acids to terminal alkynes. A careful choice of the catalytic system, substrate and carboxylic acid can provide alk-1-en-2-yl esters, alk-1-en-1-yl esters synthesis or enyne dimerization. In this way substituted isopropenol and α-methylenebenzyl formates, (geminal, geminal) dienol diesters were synthesized in one step by direct addition of formic acid or benzoic acid to terminal mono- and di-ynes.
Ring-closing metathesis, Kharasch addition and enol ester synthesis catalysed by a novel class of ruthenium(II) complexes
De Clercq, Bob,Verpoort, Francis
, p. 8959 - 8963 (2007/10/03)
Ruthenium Schiff base complexes I-III mediated the Kharasch addition of carbon tetrachloride across olefins with high yields which markedly depended on the catalyst and the substrate used. In addition, ring-closing metathesis of some representative diolefins was carried out. The best catalytic system III is able to form tri- and tetrasubstituted double bond products. Finally, dependent of the catalytic system and the reaction conditions used, these systems can catalyse the stereoselective formation of enol esters or enynes in excellent yields.
