85995-46-6

Upstream product

• 84001-90-1 (E)-ethyl 3-mesitylacrylate 
• 623-47-2 propynoic acid ethyl ester 
• 108-67-8 1,3,5-trimethyl-benzene 
• 2633-66-1 2-mesitylmagnesium bromide 

Downstream Products

• 1099654-15-5 diethyl (2E,4Z)-4-{3-[(1Z)-2-(ethoxycarbonyl)ethenyl]-2,4,6-trimethylbenzylidene}-2-pentenedioate 

Relevant academic research and scientific papers

Controlling the Properties of a 2,2′-bipy-Platinum Dichloride Complex via Oxidation of a Peripheral Stibine Moiety

Our interest in the chemistry of antimony derivatives has led us to investigate the synthesis and properties of 4-(diphenylstibino)-2,2′-bipyridine (LSbPh2). This new ligand, which could be obtained by reaction of 4-lithio-2,2′-bipyridine with Ph2SbCl, was treated with Pt(CH3CN)2Cl2 to afford the platinum complex LSbPh2PtCl2 (1). Interestingly, the latter reacts with PhICl2 to afford LSbCl2Ph2PtCl2 (2), a complex in which the peripheral stibine moiety has been converted into a dichlorostiborane. Complexes 1 and 2 have both been fully characterized. Computational, UV-vis, and cyclic voltammetry studies show that oxidation of the antimony atom leads to a lowering of the bipy-centered LUMO, indicating that 2 is more electron deficient than 1. A congruent picture emerges from reactivity studies, which show that 2 is a more active catalyst for the hydroarylation of ethyl propiolate by mesitylene.

A Y-shaped tris-N-heterocyclic carbene for the synthesis of simultaneously chelate-monodentate dipalladium complexes

A Y-shaped tris-NHC ligand has been obtained and coordinated to palladium, affording metal complexes with novel topological properties. The tris-NHC ligand is capable of coordinating the two metals, affording two different coordination environments. The X

Gold(I) Complexes in Ionic Liquids: An Efficient Catalytic System for the C-H Functionalization of Arenes and Heteroarenes under Mild Conditions

Use of ionic liquids bearing the proper counteranion as reaction solvents allows to boost the reactivity of gold(I) complexes as catalysts in the hydroarylation of alkynes with arenes and heteroarenes. Several commercial complexes of general structure LAu

Palladacycles bearing COOH-/ester-functionalized N-heterocyclic carbenes: Divergent syntheses and catalytic applications

Two new [C^N]-type palladacyclic dinuclear complexes bearing carboxylate-containing N-heterocyclic carbenes (NHCs) were synthesized, and in both cases the carboxylato-NHC ligand adopts a bridging mode. Both complexes proved to be suitable precursors, whic

Stereo- and Regioselective Addition of Arene to Alkyne Using Abnormal NHC Based Palladium Catalysts: Elucidating the Role of Trifluoroacetic Acid in Fujiwara Process

Hydroarylation of alkyne was reported by Fujiwara nearly two decades back. Interestingly, this reaction does not proceed in the absence of trifluoroacetic acid; however, the exact role of TFA has not been unambiguously established, in particular with the

Synthesis, structure and catalytic activity of a gold(i) complex containing 1,2-bis(diphenylphosphino)benzene monoxide

The gold(i) complex [Au(dppbO)Cl] was synthesized by reaction of Na[AuCl4]·2H2O with 1,2-bis(diphenylphosphino)benzene (dppb) in the presence of water. This is a new method for the synthesis of a bisphosphine monoxide gold(i) complex. The new gold(i) complex was characterized by NMR spectroscopy and X-ray crystal structure analysis. In the solid state structure a relatively short contact between the oxygen atom of the phosphine oxide group and the gold center was observed. The catalytic activity of [Au(dppbO)Cl] was tested for three different intermolecular alkyne hydrofunctionalization reactions. Silver tetrafluoroborate was used as co-catalyst for halide abstraction. While the bisphosphine monoxide gold(i) complex showed moderate activity for the hydration of various alkynes and the hydroamination of phenyl acetylene, high activity was observed for the hydroarylation of ethylpropiolate. Electron-rich arenes add very fast to the C-C triple bond but with relatively low selectivity.

Alkyne hydroarylation with Au N-heterocyclic carbene catalysts

Mono- and dinuclear gold complexes with N-heterocyclic carbene (NHC) ligands have been employed as catalysts in the intermolecular hydroarylation of alkynes with simple unfunctionalised arenes. Both mono- and dinuclear gold(III) complexes were able to catalyze the reaction; however, the best results were obtained with the mononuclear gold(I) complex IPrAuCl. This complex, activated with one equivalent of silver tetrafluoroborate, exhibited under acidic conditions at room temperature much higher catalytic activity and selectivity compared to more commonly employed palladium(II) catalysts. Moreover, the complex was active, albeit to a minor extent, even under neutral conditions, and exhibited lower activity but higher selectivity compared to the previously published complex AuCl(PPh3). Preliminary results on intramolecular hydroarylations using this catalytic system indicate, however, that alkyne hydration by traces of water may become a serious competing reaction.

Regio- and stereocontrolled reaction of arenes with ethyl propiolate catalyzed by palladium or platinum complexes with a bidentate phosphine ligand. an efficient and straightforward synthesis of (1z,3e)-1-aryl-1,3-butadienes

The reaction of mesitylene with ethyl propiolate in the presence of [Pd(dppe)(OAc)2] in TFA at 30 °C for 5 h gave diethyl (2E,4Z)-4-[(2,4,6- trimethylphenyl)methylene]-2-pentenedioate selectively. Screening several bidentate phosphines ligands showed that dppe and dppm ligands are good for the arylbutadiene formation. This reaction was applied to other electron-rich arenes and found to be effective for synthesis of arylbutadienes and extended -conjugated molecules. The regio- and stereoselective addition of an arene to propiolate was confirmed by NMR and single-crystal X-ray structural analyses of the products, suggesting that the arylbutadiene formation consisted of anti addition of an arene and a metal to the triple bond of ethyl propiolate, followed by syn addition to another molecule of ethyl propiolate. Similarly, the reaction of various arenes with ethyl propiolate in the presence of [Pt(dppe)(OTf )2] catalyst gave arylbutadienes selectively. In the Pd- or Pt-catalyzed reaction of arenes with ethyl propiolate, it was found that a bidentate ligand controlled the reaction to lead the formation of arylbutadienes.

Synthesis and structure of 1,4-diphenyl-3-methyl-1,2,3-triazol-5-ylidene palladium complexes and application in catalytic hydroarylation of alkynes

An abnormal or mesoionic N-heterocyclic carbene (NHC), namely 1,4-diphenyl-3-methyl-1,2,3-triazol-5-ylidene (Tz), formed from 1,4-diphenyl-3-methyl-1,2,3-triazolium iodide and silver oxide, gave the corresponding silver carbene complex. The transmetalatio

Catalytic hydroarylation of alkynes with arenes in the presence of FeCl3 and AgOTf

Hydroarylation of propiolic acids with various arenes in TFA proceeded efficiently in the presence of FeCl3/AgOTf catalyst system. In the case of electron-rich arenes, the iron-catalyzed hydroarylation gave cinnamic acids in moderate to high yields. The hydroarylation of phenylacetylene was observed but the catalyst was not effective under the same conditions.