Influence of phenolic compounds on the Mo(CO)6 catalysed metathetical reactions of alkynes

Vosloo, Hermanus C.M.; Plessis, J. A. K. du

doi:10.1016/s1381-1169(98)00089-2

Cited by 28 publications

(8 citation statements)

References 13 publications

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“…Such a mechanism has also been developed later to account for the production of putative metallacarbene intermediates during phenylacetylene polymerization on Mo(CO) 6 -ArOH catalysts [19].…”

Section: Mechanism Using Molybdenum/aroh Catalystsmentioning

confidence: 99%

Alkyne metathesis catalysts: Scope and future

Mortreux

Coutelier

2006

Journal of Molecular Catalysis A: Chemical

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This paper presents the evolution of alkyne metathesis since the early discoveries, essentially from the catalyst point of view. It is shown that although well defined carbynes may be useful for this reaction, further work has been made, aimed at the synthesis of new catalysts or catalytic systems, based on molybdenum precursors , associated or not with phenolic cocatalysts. The major objectives have been to obtain more functional groups tolerants catalysts, for their application in organic synthesis, including RCM for further stereoselective hydrogenation of the triple bond in the cycle, as well as for polymerization of aromatic diynes. Some insights into the possible mechanisms are given, and data relevant to the metathesis of terminal alkynes, a still challenging reaction where polymerization is occurring via the formation of deprotonated metallacyclobutadiene, are also presented and discussed.2

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Section: Mechanism Using Molybdenum/aroh Catalystsmentioning

confidence: 99%

Alkyne metathesis catalysts: Scope and future

Mortreux

Coutelier

2006

Journal of Molecular Catalysis A: Chemical

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“…Nonetheless, limitations include low functional group tolerance, low conversions and the need for high reaction temperatures. [13][14][15][16][17][18][19][20][21][22][23][24][25] The mechanism of alkyne metathesis was not quite understood until T. J. Katz suggested an alkylidyne complex as thea ctive speciesa nd an intermediate metallacyclobutadiene complex (MCBD)f ormed in a[ 2 + +2] cycloaddition (Scheme 1). [26] The product and an ew alkylidyne species are liberated upon cycloelimination.…”

Section: Introductionmentioning

confidence: 99%

“…[33] Schrock's catalyst 3 has been studied thoroughly for many years and hasf ound broad use in ring-closing alkyne metathesis (ROAMP) and in the total synthesis of natural products. [34,35,36] Considering that initial results in alkyne metathesis stemmed from ill-defined Mo(CO) 6 systems, [13][14][15][16][17][18][19][20][21][22][23][24][25] studies were soon directed towards molybdenuma lkylidyne complexes. Molybdenum neopentylidyne complexesw ith fluoroalkoxy ligands were found to be active in alkyne metathesis, whereas the tertbutoxide complex [tBuCMo(OtBu) 3 ]o nly furnished poor yields.…”

Section: Introductionmentioning

confidence: 99%

Well‐Defined Alkyne Metathesis Catalysts: Developments and Recent Applications

Ehrhorn

Tamm

2018

Chemistry A European J

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Although alkyne metathesis has been known for 50 years, rapid progress in this field has mostly occurred during the last two decades. In this article, the development of several highly efficient andt horoughly studied alkyne metathesis catalysts is reviewed, which includes novel welldefined, in situ formed and heterogeneous systems. Various alkyne metathesis methodologies, including alkyne crossmetathesis (ACM), ring-closing alkyne metathesis (RCAM), cy-clooligomerization,a cyclic diyne metathesis polymerization (ADIMET), and ring-opening alkyne metathesis polymerization (ROAMP), are presented, and their application in natural product synthesis, materials science as well as supramolecular and polymer chemistry is discussed. Recent progress in the metathesis of diynes is also summarized, which gave rise to new methods such as ring-closing diyne metathesis (RCDM)a nd diyne cross-metathesis(DYCM). Scheme1.Mechanism of alkyne metathesis.Scheme2.Synthesis of Schrock's tungsten alkylidyne complex 3.[a] H. Ehrhorn, Prof. Dr.M.T amm Scheme9.Synthesis of molybdenumb enzylidynecomplexes 22 with triphenylsilanolate ligands ;phen = 1,10-phenanthroline.Scheme10. Synthesis of trisilanolate tungsten and molybdenum benzylidyne complexes 25.

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“…Since then many catalytic systems based on molybdenum carbonyl compounds and various phenols have been described, and a number of applications of alkyne metathesis in organic synthesis have been discovered [27][28][29][30][31][32][33][34][35][36][37][38]. In 2006, Mortreux and Coutelier published a review of these advances, covering the literature up to and including 2005 [27].…”

Section: B Metathesis Of Alkynesmentioning

confidence: 99%

“…A very interesting reaction initiated by molybdenum(0) carbonyl complexes (in the presence of phenols) is the polymerization of terminal alkynes leading to the formation of polyenic polymers (Scheme 8) [28,29,31]. This reaction was first observed by Woon Mo(CO) 6 and Farona in 1974, in the presence of the molybdenum arene complex [Mo(CO) 3 ( 6 -toluene)] [39].…”

Section: C Metathesis Polymerization and Cyclotrimerization Of Alkmentioning

confidence: 99%

Carbonyl Complexes of Molybdenum and their Catalytic Activity

Szymańska-Buzar

2012

COC

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This is a review of the published papers that focus on the reactivity of carbonyl complexes of molybdenum in low oxidation states (usually zero or two) and possible applications of molybdenum complexes as precursors of catalysts in different reactions of unsaturated organic substrates such as alkenes and alkynes. The following reactions are analyzed: metathesis, metathesis polymerization, free radical reactions of alkenes, hydrogenation, hydrosilylation, hydrogermylation, hydrostannation, hydroarylation, asymmetric allylic alkylation, and epoxidation. In addition to the interesting practical aspects of these catalytic reactions, they provide additional insights into molybdenum chemistry.

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Influence of phenolic compounds on the Mo(CO)6 catalysed metathetical reactions of alkynes

Cited by 28 publications

References 13 publications

Alkyne metathesis catalysts: Scope and future

Alkyne metathesis catalysts: Scope and future

Well‐Defined Alkyne Metathesis Catalysts: Developments and Recent Applications

Carbonyl Complexes of Molybdenum and their Catalytic Activity

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