Palladium heterocycles

Four-membered heterocycles can be formed by the addition of isocyanides to 1,3-dipoles (80AG(E)45) and by the reaction of carbon monoxide with -haloamines, with the aid of palladium catalysis (Scheme 10) (79CC699). 

Allylic protection groups and their removal through catalytic palladium rr-allyl methodology in transformations of heterocycles 98T2967. [3- -3]Benzannelation of heteroaromatics consisting of successive nucleophilic... 

Palladium(0)-catalyzed allylation of ambident nucleophilic aromatic heterocycles 96AHC(66)73. 

Allylic protection groups and their removal through catalytic palladium Tr-allyl methodology in synthesis of heterocycles 98T2967. 

Palladium(II)-catalyzed cyclization of N-alkylation of allyl alcohols by ure-tanes and its application to the synthesis of natural saturated heterocycles 98YGK34. 

Shaw concluded that hydrogenation of 3-alkyl-4-aminomethylene isoxazol-5-ones (184) in the presence of palladium catalyst resulted in the saturation of either the endocyclic double carbon-nitrogen bond or the exocyclic double C—C bond with the retention of the heterocyclic nitrogen-oxygen bond. Recent data reported by Kochetkov et al. on the properties, and in particular on hydrogenation, of isoxazolid-5-ones - indicate, however, that Shaw had probably ob-... 

Cacchi and Palmier (83T3373) investigated a new entry into the quinoline skeleton by palladium-catalyzed Michael-type reactions. They found that phenyl mercurial 134 was a useful intermediate for the synthesis of quinoline derivatives, and that by selecting the reaction conditions the oxidation level of the heterocyclic ring in the quinoline skeleton can be varied. On such example is shown in Scheme 16. PdCla-catalyzed coupling between organomercurial reagent 134 and enone 135 delivered adduct 136 which was subsequently cyclized to quinoline 137 under acidic conditions. 

In the first chapter, N. M. Ahmad and J. J. Li (Pfizer, Ann Arbor, USA) discuss the use of palladium in quinoline synthesis, thus filling an important gap in a recent monograph on the uses of palladium catalysis in heterocyclic synthesis authored by the same group. This is followed by an account of pyrimidine-pyridine interconversions by H. C. van der Plas (Wageningen University, The Netherlands) the immense variety of heterocyclic chemistry is illustrated by the large number of diverse strategies for such transformations. 

Harrwig and Bnchwidd have developed a new methodology for aryladon of amines or phenols with aryl halides and palladium catiilysts This reacdon provides a very useful strategy for the preparadon of various heterocyclic compounds such as phenazines, as shown in Scheme... 

As well as phosphorus ligands, heterocyclic carbenes ligands 10 have proven to be interesting donor ligands for stabilization of transition metal complexes (especially palladium) in ionic liquids. The imidazolium cation is usually presumed to be a simple inert component of the solvent system. However, the proton on the carbon atom at position 2 in the imidazolium is acidic and this carbon atom can be depro-tonated by, for example, basic ligands of the metal complex, to form carbenes (Scheme 5.3-2). 

The ease of formation of the carbene depends on the nucleophilicity of the anion associated with the imidazolium. For example, when Pd(OAc)2 is heated in the presence of [BMIM][Br], the formation of a mixture of Pd imidazolylidene complexes occurs. Palladium complexes have been shown to be active and stable catalysts for Heck and other C-C coupling reactions [34]. The highest activity and stability of palladium is observed in the ionic liquid [BMIM][Brj. Carbene complexes can be formed not only by deprotonation of the imidazolium cation but also by direct oxidative addition to metal(O) (Scheme 5.3-3). These heterocyclic carbene ligands can be functionalized with polar groups in order to increase their affinity for ionic liquids. While their donor properties can be compared to those of donor phosphines, they have the advantage over phosphines of being stable toward oxidation. 

The Suzuki reaction has been successfully used to introduce new C - C bonds into 2-pyridones [75,83,84]. The use of microwave irradiation in transition-metal-catalyzed transformations is reported to decrease reaction times [52]. Still, there is, to our knowledge, only one example where a microwave-assisted Suzuki reaction has been performed on a quinolin-2(lH)-one or any other 2-pyridone containing heterocycle. Glasnov et al. described a Suzuki reaction of 4-chloro-quinolin-2(lff)-one with phenylboronic acid in presence of a palladium-catalyst under microwave irradiation (Scheme 13) [53]. After screening different conditions to improve the conversion and isolated yield of the desired aryl substituted quinolin-2( lff)-one 47, they found that a combination of palladium acetate and triphenylphosphine as catalyst (0.5 mol %), a 3 1 mixture of 1,2-dimethoxyethane (DME) and water as solvent, triethyl-amine as base, and irradiation for 30 min at 150 °C gave the best result. Crucial for the reaction was the temperature and the amount of water in the... 

Abstract A literature overview, up to the end of 2004, of the most important microwave-assisted transition-metal-mediated processes used for the decoration and construction of heterocycles is presented. The emphasis of the chapter lies in the use of palladium-assisted reactions but examples of copper- and nickel-mediated processes are also incorporated. 

Independently, Caddick et al. reported microwave-assisted amination of aryl chlorides using a palladium-N-heterocyclic carbene complex as the catalyst (Scheme 99) [lOlj. Initial experiments in a domestic microwave oven (reflux conditions) revealed that the solvent is crucial for the reaction. The Pd source also proved very important, since Pd(OAc)2 at high power in DMF gave extensive catalyst decomposition and using it at medium and low power gave no reaction at all. Pd(dba)2/imidazohum salt (1 mol% catalyst loading) in DME with the addition of some DMF was found to be suitable. Oil bath experiments indicated that only thermal effects are governing the amination reactions. 

Nolan SP, Viciu MS (2005) The Use of N-Heterocyclic Carbenes as Ligands in Palladium Mediated Catalysis. 14 241-278... 

Palladium-catalyzed substitution can also be applied to nonbasic nitrogen heterocycles, such as indoles, in the absence of strong bases. 

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