Catalysis allylic alkylation

One of the main applications of dendrimers is in catalysis allowing easy recycling of the homogeneous catalyst by means of nanofiltration. Carbosilane dendrimers functionalized with diphenylphosphine groups at the periphery have been synthesized and characterized. Palladium complexes of these dendrimers have been used as catalysts in the allylic alkylation reaction. These dendrimeric catalysts can be used in a continuous process using a membrane reactor.509... 

Keywords Allylic Alkylation m Asymmetric Catalysis m C2-Symmetry m De-symmetrization m Electronic Differentiation m Heck Reaction m Hydrogenations m Metal Complexes m Modular Design m P,N-Ligands m Steric Differentiation m Respective Control... 

As many endeavors in transition-metal catalysis, the design, synthesis and screening of chiral ligands have played a pivotal role in the development of the asymmetric allylic alkylation reaction. A series of C2-symmetric diphosphines such as DiPAMP, chiraphos, DIOP. and BINAP,... 

The formation of a branched chiral product from the alkylation of monosubstituted substrates is not limited to the catalysis of metals described thus far. Allylic alkylation reactions catalyzed with rhodium [211] and iridium [212] complexes have been shown to occur at the more... 

Although mechanistically different, a successful kinetic resolution of cyclic allyl ethers has recently been achieved by zirconium catalysis [2201. Other metals such as cobalt [221], ruthenium [222], and iron [2231 have been shown to catalyze allylic alkylation reactions via metal-allyl complexes. However, their catalytic systems have not been thoroughly investigated, and the corresponding asymmetric catalytic processes have not been forthcoming. Nevertheless, increasing interest in the use of alternative metals for asymmetric alkylation will undoubtedly promote further research in this area. 

Direct catalytic intermolecular a-allylic alkylation of aldehydes and cyclic ketones has been achieved using a one-pot combination of a transition metal catalyst, Pd(PPh3)4, and an organocatalyst a secondary amine which facilitates enamine catalysis.300... 

A simple method for the direct catalytic allylic alkylation of aldehydes and cyclic ketones has been developed.26 The direct catalytic highly chemo- and regio-selective intermolecular a-allyhc alkylation reaction has been mediated by an unprecedented combination of palladium and enamine catalysis which furnishes a-allylic alkylated aldehydes and cyclic ketones in high yield. 

With 1-alkoxyallenes as proelectrophiles, the palladium-catalysed asymmetric allylic alkylation proceeds with 1,3-dicarbonyl compounds as pronucleophiles with excellent regioselectivity good enantioselectivity (82-99% ee) was obtained with the Trost lig- and. The pH of the medium proved crucial for the reactivity and selectivity. By using the more acidic Meldrum s acids, the reactions required a co-catalytic amount of a Brpnsted acid, such as CF3CO2H. On the other hand, the less acidic 1,3-diketones failed to react under these conditions but the reaction proved to occur in the presence of the weaker benzoic acid, suggesting the need for general base catalysis. Indeed, a mixture of Et3N and PhCOiH proved to be optimal (93-99% ee). A mechanistic model to rationalize these results has been developed.88... 

The synthesis of quaternary amino acids 86 have been shown using azlac-tones 85 as nucleophiles and the Trost ligand 39 under palladium [179] or molybdenum catalysis (Scheme 8) [180]. The allylic alkylation of glycine imino esters under biphasic conditions has also been achieved using a chiral phase-transfer catalyst in combination with an achiral Pd catalyst producing the unnatural amino acid derivatives [181]. 

The supramolecular binding motifs described here were also used to attach catalysts to solid (silica) supports (128). The active metal complex could be switched from palladium to rhodium by using a polar solvent that breaks up the binding of the supramolecular motif. Allylic alkylation and hydroformylation catalysis could be carried out by using the same support "receptor" material and different "guest" ligands for the two metals a... 

These hydroxy-1,1 -binaphthyl functionalised NHC ligands can be used in asynunetric catalysis. Catalytic reagents performed with transition metal catalysts carrying these ligands include olefin metathesis [19,80,86], allylic alkylation [17,18,88] and hydrosilylation of ketones [85]. 

There are a number of metal-ligand systems that will provide the proper activation for nucleophile coupling, but the Pd system is by far the most well developed and useful. In recent years, asymmetric allylic alkylation reactions have received the most interest for organic synthesis apphcations (see Asymmetric Synthesis by Homogeneous Catalysis). Metals other than Pd have also received some additional attention. 

Ruthenium-catalyzed allylic alkylation falls between known catalysis with respect to regioselectivity and chirality of products. Like Pd, Mo, and W-but unlike Rh regioselectivity is not highly dependent on the nature of the starting carbonate. However, unlike Pd and Mo, but similar to Rh and W, substitution of the chiral substrate occurs with high retention of configuration, (equation 75). Hence the Ru system compliments other metal-catalyzed allylic systems well. ... 

The formation of allenylidene derivatives from ethynyl-hexanol and alkenyl-vinylidene mononuclear complexes (9), the formation of mononuclear ruthenium allenyl complexes from terminal alkynes (10), the intermediacy of ruthenium-allenylidene complexes in forming propargylic alcohols (II), and in the cyclization of propargyl alcohols (12), and the use of mononuclear ruthenium compounds in allylic alkylation catalysis (13) have also been reported. 

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