Palladium reactions catalysed

Transition metal-catalysed reactions are probably the most rapidly expanding area in organic chemistry at present and they have been used extensively in both the ring synthesis and the functionalisation of heterocycles. As well as completely new modes of reactivity, variants of older synthetic methods have been developed using the milder and more selective processes which attach to the use of transition metal catalysts. Palladium is by far the most important and widely used catalyst due to the very wide range of reaction types in which it can function. Nickel catalysts (mechanistically similar to palladium) have also been used, but for a narrower range of reactions. 

Palladium-catalysed processes typically utilise only 1-5 mol% of the catalyst and proceed through small concentrations of transient palladium species there is a sequence of steps, each with an organopalladium intermediate, and it is important to become familiar with these basic organopalladium processes in order to rationalise the overall conversion. Concerted, rather than ionic, mechanisms are the rule so it is misleading to compare them too closely with apparantly similar classical organic mechanisms, however curly arrows can be used as a memory aid (in the same way as one may use them for cycloaddition reactions), and this is the way in which palladium-catalysed reactions are explained in the following discussion. 

Note For clarity, ligands which are not involved in the transformation under consideration are omitted from the following schemes, however it is important to understand that most organopalladium compounds normally exist as 4-coordinate, square-planar complexes  

Despite an apparent similarity between RPdX and RMgX, their chemical properties are very different. The former are usually stable to air and water and unreactive to the usual electrophilic centres such as carbonyl, whereas RMgX do react with oxygen, water, and carbonyl compounds. 

Organopalladium species with two organic units attached to the metal, R PdR, are generally unstable extrusion of the metal, in a zero oxidation state, takes place, with the consequent linking of the two organic units. Because this is again a concerted process, stereochemistry in the organic moiety(ies) is conserved. 

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B By palladium-catalysed reaction with amidoacrylate esters... 

Carbon-carbon bond formation reactions and the CH activation of methane are another example where NHC complexes have been used successfully in catalytic applications. Palladium-catalysed reactions include Heck-type reactions, especially the Mizoroki-Heck reaction itself [171-175], and various cross-coupling reactions [176-182]. They have also been found useful for related reactions like the Sonogashira coupling [183-185] or the Buchwald-Hartwig amination [186-189]. The reactions are similar concerning the first step of the catalytic cycle, the oxidative addition of aryl halides to palladium(O) species. This is facilitated by electron-donating substituents and therefore the development of highly active catalysts has focussed on NHC complexes. 

A review of the palladium-catalysed reactions of halo-pyridazines has been published <06SL3185>. 

A number of palladium-catalysed reactions of the triflate 61 have been reported but the nucleophilic displacement with primary aliphatic amines was, surprisingly, very slow in refluxing THF (24-92h). However, under microwave irradiation the reactions were very rapid and gave high yields, although even with microwaves, secondary amines and anilines failed to... 

Palladium-catalysed C-C bond formation under Heck reaction conditions, which normally requires anhydrous conditions and the presence of copper(I) salts, is aided by the addition of quaternary ammonium salts. It has been shown that it is frequently possible to dispense with the copper catalyst and use standard two-phase reactions conditions [e.g. 18, 19]. Tetra-/i-butylammonium salts catalyse the palladium-catalysed reaction of iodoarenes with alkynes to yield the arylethynes in high yield [20, 21], whereas the reaction with 3-methylbut-1 -yn-3-ol (Scheme 6.30) provides a route to diarylethynes [22]. Diarylethynes are also formed from the reaction of an iodoarene with trimethylsilylethyne [23], Iodoalkynes react with a,p-unsaturated ketones and esters to produce the conjugated yne-eneones [19],... 

P-Phenylation of a,p-unsaturated ketones in high yield (75-85%), using the palladium catalysed reaction with phenylmercury(II) chloride or tetraphenyltin(IV), is promoted by tetra-n-butylammonium chloride [37],... 

The inclusion of the allyl moiety in an appropriate ring system led to the formation of a new, chiral quaternary carbon center (3.13.), By the use of optically active starting material, Mori and co-workers were able to control the stereochemistry of the new chiral centre (N.B. the chirality of the first centre was also set by a palladium catalysed reaction, the Tsuji-Trost allylation).17... 

The rate of formation of pairs of vinyls will be proportional to the hydrogen pressure and hence the rate of formation of ethylene by step (8) will be first order in hydrogen. An alternative mechanism for the palladium-catalysed reaction involving the reaction of adsorbed acetylene with molecular hydrogen has been proposed [9]. 

Mechanism B was originally proposed for the palladium-catalysed reaction [208], which is characterised by a high trans cis ratio. In this mechanism, conformational interconversion of adsorbed species does not occur and the trans cis ratio is a direct reflection of the relative surface concentrations of the anti- and syn-diadsorbed buta-1 3-diene, which are dependent upon the nature of the sites available at the surface and upon the relative stabilities of the two conformers. In addition to palladium, mechanism B has been proposed, along with a contribution from mechanism A,... 

From these results it can be seen that in the hydrogenation of 1,2-dialkylcyclohexenes the expected cis-1,2-dialkylcyclohexane is not the sole product. Similarly, in the hydrogenation of the 1,4-dialky lcyclohexenes where both the cis- and trans-cyclohexanes are expected, the trans-isomer being the thermodynamically more stable, the stereoselectivity varies from metal to metal. Thus with palladium, the cis/trans ratio approaches the equilibrium composition, whereas with platinum and rhodium, the equilibrium composition is never approached. It is also instructive to note that in the palladium-catalysed reactions, hydrogenation is accompanied by extensive alkene isomerisation [220—223], whereas with rhodium and platinum, little or no isomerisation is observed [220,... 

Villemin, D. and Caillot, F., Microwave mediated palladium-catalysed reactions on potassium fluo-ride/alumina without use of solvent, Tetrahedron Lett., 2001, 42, 639-642. 

Palladium catalysts have been found which are effective in the Suzuki coupling reaction of arylboronic acids with aryl chlorides carrying electron-withdrawing groups.73 Biaryls may also be synthesized by cross-coupling of arylboronic acids with arenediazonium salts.74,75 There has been a report of the polymer-bound palladium-catalysed Suzuki coupling of aryl triflates with organoboron compounds.76 Arylbor-onates may themselves be synthesized by the palladium-catalysed reactions of... 

It has been found that the use, as ligands, of electron-poor phosphines, such as 1,1 -bis(diphenylphosphino)ferrocene, enhances yields ill the palladium-catalysed reaction of aiyl bromides with sodium phenoxides to yield diaryl ethers.87 Palladium-catalysed coupling of ethynylated derivatives of bipyridine or terpyridine with the corresponding bipyridine or terpyridine hahdes or triflates has been used in the synthesis of preorganized polytopic ligands.88... 

The Heck reaction has now been reviewed448,449. Evidence for the formation of zerova-lent palladium from (AcO Pd and Ph3P via a redox process has been provided450. This explains the origin of Pd(0) required for certain palladium-catalysed reactions in cases where Pd(II) is added to the reaction as the primary form of the Pd-catalyst. Thallium has been found to accelerate the Heck-type cyclization-carbonylation451. 

A procedure has been developed for the palladium-catalysed a-arylation of amides by aryl bromides using the zinc enolates of the amides. The reaction works well with bromoarenes carrying a variety of ring substituents and with bromopyridine. In addition, the reaction has been shown to be effective with morpholine amides to give products which are precursors for aldehydes and ketones.39 A new method has been reported for the allylation of aryl halides using homoallyl alcohols as the allyl source the palladium-catalysed reaction, which may be both stereo- and regio-sepecific, uses a retro-allylation reaction to form a a-allyl(aryl)palladium intermediate.40... 

Palladium-catalysed reactions of dimetallic compounds 358 such as X2B—BX2, R3Sn—SnR3, R3S11—SiR3 or R3Si—SiR3 with halides via oxidative addition and transmetallation are useful for the preparation of carbon main group metal bonds 359. 

However, for other palladium catalysed reactions of organozinc iodides with electrophiles, THF is a good choice of solvent. The incompatibility of THF and acid chlorides at ambient temperature can also be overcome, in some cases, by the use of a carbonylative cross-coupling in which an iodobenzene derivative is used as the precursor.17... 

Palladium catalysed reaction of cinnamaldehyde with allyl benzoate and diethylzinc to produce ( )-1-phenyl-1,S-hexadien-3-ol66... 

The palladium-catalysed addition of aryl, vinyl, or substituted vinyl groups to organic halides or triflates, the Heck reaction, is one of the most synthetically useful palladium-catalysed reactions. The method is very efficient, and carries out a transformation that is difficult by more traditional techniques. The mechanism involves the oxidative addition of the halide, insertion of the olefin, and elimination of the product by a p-hydride elimination process. A base then regenerates the palladi-um(0) catalyst. The whole process is a catalytic cycle. 

S. Explain why enantiomerically pure lactone gives all syn but racemic product in this palladium-catalysed reaction. 

The synthesis of an antifungal drug was completed by tl palladium-catalysed reaction. Give a mechanism and explain t regio- and stereoselectivity. 

A synthesis of the natural product y-lycorane starts with a palladium-catalysed reaction. What sort of a reaction is this, and how does it work ... 

For a review on the palladium-catalysed reaction of organotin compounds, see T. N. Mitchell, Synthesis, 1992, 9, 803. 

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