Palladacycle catalysts, Heck reaction

Although only a dozen known metal complexes were tested in this manner, proof of principle was demonstrated. The test revealed Wilkinson s catalyst to be the most active hydrosilylating agent, its use in this type of reaction being known. However, the study also led to the discovery that a palladacycle, [Pd (o-tolyl)2PC6H4 (OAc)]2, which is usually considered to be potent in Heck reactions, is also an excellent hydrosilylation catalyst.37,38 Control experiments showed that the relative order of catalyst activity is the same when conventional substrates are used in place of the dyes (8). 

In a recent article by Botella and Najera, controlled mono- and double-Heck arylations in water catalyzed by an oxime-derived palladacycle were described [22], When the reaction was carried out under microwave irradiation at 120 °C in the presence of dicyclohexylmethylamine with only 0.01 mol% of palladium catalyst (palladium acetate or palladacycle), monoarylation took place in only 10 min with a very high turnover frequency (TOF) of > 40000 (Scheme 6.3). As regards diarylation, 1 mol% of the palladacycle catalyst and 2 equivalents of iodobenzene had to be utilized to obtain moderate to good yields of diarylated product. Whereas microwave heating at 120 °C provided a 31% yield after 10 min, a 66% isolated yield of product was obtained by heating the reaction mixture under reflux for 13 h at 100 °C. Here, the... 

Gruber AS, Zim D, Ebeling G, Monteiro AL Dupont (2000) Sulfur-containing palladacycles as catalyst precursors for the Heck reaction. J Org Lett 2 1287-1290... 

Herrmann WA, Brossmer C, Reisinger CP, Riermaier T, Ofele K, Beller M (1997) Coordination chemistry and mechanisms of metal-catalyzed C-C coupling reactions. Part 10. Palladacycles efficient new catalysts for the Heck vinylation of aryl halides. Chem Eur J 3 1357-1364 Iyer S, Jayanthi A (2001) Acetylferrocenyloxime palladacycle-catalyzed Heck reactions. Tetrahedron Lett 42 7877-7878 Iyer S, Ramesh C (2000) Aryl-Pd covalently bonded palladacycles, novel amino and oxime catalysts di- x-chlorobis(benzaldehydeoxime-6-C,AT)dipalla-dium(II), di- x-chlorobis(dimethylbenzylamine-6-C,A)dipalladium(II) for the Heck reaction. Tetrahedron Lett 41 8981-8984 Jeffery T (1984) Palladium-catalysed vinylation of organic halides under solid-liquid phase transfer conditions. J Chem Soc Chem Commun 1287-1289 (b) idem,... 

Rawal s group developed an intramolecular aryl Heck cyclization method to synthesize benzofurans, indoles, and benzopyrans [83], The rate of cyclization was significantly accelerated in the presence of bases, presumably because the phenolate anion formed under the reaction conditions was much more reactive as a soft nucleophile than phenol. In the presence of a catalytic amount of Herrmann s dimeric palladacyclic catalyst (101) [84], and 3 equivalents of CS2CO3 in DMA, vinyl iodide 100 was transformed into ortho and para benzofuran 102 and 103. In the mechanism proposed by Rawal, oxidative addition of phenolate 104 to Pd(0) is followed by nucleophilic attack of the ambident phenolate anion on o-palladium intermediate 105 to afford aryl-vinyl palladium species 106 after rearomatization of the presumed cyclohexadienone intermediate. Reductive elimination of palladium followed by isomerization of the exocyclic double bond furnishes 102. 

As detailed elsewhere, the fluorous palladacycle acetates and hahdes 7 and 8 were synthesized [38,39]. These feature three Rfg ponytails, and were poorly soluble in common organic solvents at room temperature, and insoluble in DMF. However, they were very soluble in DMF at higher temperatures. All were effective catalyst precursors for Heck reactions (100-140 °C), and precipitated (as the halides) upon cooling. However, a number of control experiments established that 7 and 8 served as steady-state sources of colloidal palladium nanoparticles, formed anew with each cycle imtil the palladacycles were exhausted. These, or low-valent Pd(0) species derived therefrom, were the true catalysts. 

Palladacycles, such as (80), derived from tri(l-naphthyl)phosphine, proved to be very active catalysts for Heck reactions to produce (81) (ArX = Phi, 4-MeCOC6H4Br,... 

Iyer, S. Ramesh, C. Aryl-Pd covalently bonded palladacycles, novel amino and oxime catalysts for the Heck reaction. Tetrahedron Lett. 2000, 41, 8981-8984. 

Palladacycles [17] have been established as important class of catalysts, an unusual phosphine-free sulfur containing catalyst was introduced by Zim [18] et al. A phosphinite based palladacycle [19] proved to be very efficient in Suzuki coupling reactions. An N,P-Ligand type was synthesized by Kocovsky [20] et al. Tridentate pincer ligands [21] have been proved use-fill in the Heck reaction. Recent developments regarding Heck (22] and Suzuki [23] reactions have been reviewed by Fu and Littke. A new catalyst especially suitable for Heck couplings has been introduced by Beller [24] et al. 

Crabtree and coworkers used the disappearance of color to monitor the activity of 12 potential catalysts for hydrosilation reactions [6], The group used alkenes and imines with ferrocenyl and pyrimidyl substituents at either end as colored reactants. On hydrosilation the color is bleached, because conjugation between the electron donor and acceptor groups is reduced. The bleaching is easily observed by eye and can be recorded quantitatively by means of a digital camera (Figure 5.4.1). By use of this method, the known Wilkinson catalyst was identified in a proof-of-concept experiment. A palladacycle, [ Pd (o-tolylfi PQ H4 OAc 2, usually used in Heck reactions, was also found to be catalytically active. 

Rosner, T., Le Bars, J., Pfaltz, A., Blackmond, D. G. Kinetic Studies of Heck Coupling Reactions Using Palladacycle Catalysts ... 

Oxitne-derived palladacycles act as efficient catalysts for the Heck reaction [132], They could be isolated and are found to be thermally stable, not sensitive to air or moisture, and were readily prepared from inexpensive starting material. This was exemplified in the reaction catalyzed by 376 to prepare 377 from 3 and 375. 

Scheme 2 Heck reaction with palladacycles as catalysts...

The increase of the catalyst turnover numbers is indeed one other major area where further improvements could be expected. Such improvements have recently been achieved for the standard Heck reaction by the use of high pressure conditions [86], the use of preformed palladacycles as catalysts [87], or by using a macrocyclic tetraphole as hgand [88].Dendritic diphosphine-palladium complexes as catalysts for Heck reactions have also been reported to possess superior stabihty compared to the monomeric parent compounds [89]. Transferring such iimovations to the AHR remains an important goal. 

Polystyrene-supported soluble palladacycle catalyst as recyclable catalyst for Heck, Suzuki and Sonogashira reactions... 

A new type of soluble polystyrene-supported palladium complex was synthesised (Figure 6.1) as an excellent and recyclable palladacycle catalyst for carbon-carbon bond formation in Heck, Suzuki and Sonogashira reactions to give high yields of the desired products. 

The newly invented polystyrene-supported palladacycle catalyst was prepared in six steps with high yields. The simple precipitation and filtration process to recycle the catalyst after model reactions for Heck, Suzuki, and Sonogashira reactions is noteworthy.[1]... 

Note that palladacycles typified by 2 are poisoned by 1,4-dienes, in contrast to other Pd(0) catalyst systems. Accordingly, the Heck reaction cannot employ these catalysts. On the other hand, 3 has a high thermal stability and broad scope of application (aryl couplings). Complex 4 is also a highly active catalyst for the Heck reaction (3 examples,... 

Other stable and efficient catalysts for the Heck reaction are pyrazole- and benzothia-zole-based palladacycles. They are capable of promoting Barbier-type reactions. Note that palladacycles derived from aromatic imines decompose to form metallic Pd as the active species. ... 

The search for more stable or more reactive catalysts has produced many new leads. One of the most promising is represented by the palladacycle (14), known as Hermann s catalyst. This can be used in Heck reactions at high temperatures (above 140 °C), which leads to high turnover numbers of up to 10 with electron-poor aryl bromides. 

Also worth mentioning here are studies based around the preparation and use of silica-supported palladacyclic complexes. It was the use of these that gave valuable evidence for the decomposition of half-pincer and SCS pincer " complexes during Heck reactions, generating soluble Pd(0) species that are the true catalysts. 

More recently, Najera et al. performed a number of Heck reactions of deactivated aryl halides and styrenes under phosphane-free conditions using oxime-derived palladacycles or palladium acetate as catalyst [113], Coupling can be performed either vith chcyclohexylmethylamine as base and TBAB as PTC catalyst or in neat vater vith triethylamine in N,N-dimethylacetamide (DMA) solutions under the action of MW irradiation. 

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