Palladium structure

While the formation of the palladium species was shown to be fast (and in better than 90% yield), the kinetically less labile platinum(II) ion initially gave a mixture of oligomers however, these kinetic products slowly rearranged (over a month) to the required thermodynamic product 9. Models predict that free rotation of the 4,4 -bipyridine units is restricted such that they will prefer to be orientated perpendicular to the plane of the square such an arrangement has been confirmed for the above tetra-palladium structure. ... 

M Wagner, K Kohler, L Djakovitch, S Weinkauf, V Hagen, M Muhler. Heck reactions catalyzed by oxide-supported palladium - structure-activity relationships. Topics in Catal 13 319-326, 2000. 

Allylic acetoxy groups can be substituted by amines in the presence of Pd(0) catalysts. At substituted cyclohexene derivatives the diastereoselectivity depends largely on the structure of the palladium catalyst. Polymer-bound palladium often leads to amination at the same face as the aoetoxy leaving group with regioselective attack at the sterically less hindered site of the intermediate ri -allyl complex (B.M. Trost, 1978). 

R. Hicks and co-workers, Structure Sensitivity of Methane Oxidation overl latinum and Palladium J. Catal, 280—306 (1990). 

A different type of tautomeric relationship exists between compounds of types 323 and 324. Both types of structure can be isolated, pyridones (324, Z = N—Me) and pyrones (324, Z = 0) being formed when 323 (Z = N—Me or 0) is heated with palladium on charcoal in ethylene glycol. Similar isomerizations in the quinol-4-one series have been reported."... 

Catalytic dehydrogenation using palladium/maleic acid has been used to convert tetrahydro-j8-earbolines of general structure 142 into the dihydro-jS Carbolinium salts (143) A similar transformation has been carried out by oxidation with iodine. ... 

Hi) Dehydrogenation. j3-Carboline derivatives may be obtained from tetrahydro-)3-carbohnes by zinc dust distillation or high temperatmre dehydrogenation with selenium or palladium black. Many of the complex indole alkaloids may be degraded, with bond cleavage, to yield simple )3-carbolines under these conditions and this approach has become a standard method in structural elucidations. Examples are numerous but outside the scope of this review. 

The first example of an indolo[2,3-a]carbazole derivative reported with a reasonably estabhshed structure was the mono N-methylated system 9, prepared via dehydrogenation with palladium on charcoal of the octahydro derivative 10, available via reaction of the aminocarbazole 11 with 2-hydroxycyclohexanone in the presence of a trace amount of anihnium bromide (Scheme 1). An approach toward the parent compound 1 using the same method has also been attempted, although without success (56JCS4783). The utility of this route is impaired by the complexity of the starting material, which requires multistep preparation, and the harsh conditions of the final step. 

Reaction of -picoline with a nickel-alumina catalyst has been reported to give a mixture of four isomeric dimethylbipyridines, one of which has been identified at 6,6 -dimethyl-2,2 -bipyridine. With palladium-on-carbon, 2,4-lutidine was found to be more reactive than pyridine,and the isolated biaryl has been assigned the structure (2). However, some confusion arises from the statement that this... 

Several products other than 2,2 -biaryls have been isolated following reaction of pyridines with metal catalysts. From the reaction of a-picoline with nickel-alumina, Willink and Wibaut isolated three dimethylbipyridines in addition to the 6,6 -dimethyl-2,2 -bipyridine but their structures have not been elucidated. From the reaction of quinaldine with palladium-on-carbon, Rapoport and his co-workers " obtained a by-product which they regarded as l,2-di(2-quinolyl)-ethane. From the reactions of pyridines and quinolines with degassed Raney nickel several different types of by-product have been identified. The structures and modes of formation of these compounds are of interest as they lead to a better insight into the processes occurring when pyridines interact with metal catalysts. 

Organonickel derivatives also offer cases of the -coordination of the substituted hydrotrisfpyrazol- l-yl)borate ligand. For the palladium and platinum complexes, the M(II) M(IV) (M = Pd, Pt) transformation is facile. Organopalla-dium chemistry offers anew type of agostic interactions, C—H - - - Pd, where the C—H bond belongs to one of the pyrazolate rings. Cyclopalladation of various pyrazol-l-ylborates and -methanes does not modify their structure. 

Intramolecular cycloadditions of substrates with a cleavable tether have also been realized. Thus esters (37a-37d) provided the structurally interesting tricyclic lactones (38-43). It is interesting to note that the cyclododecenyl system (w = 7) proceeded at room temperature whereas all others required refluxing dioxane. In each case, the stereoselectivity with respect to the tether was excellent. As expected, the cyclohexenyl (n=l) and cycloheptenyl (n = 2) gave the syn adducts (38) and (39) almost exclusively. On the other hand, the cyclooctenyl (n = 3) and cyclododecenyl (n = 7) systems favored the anti adducts (41) and (42) instead. The formation of the endocyclic isomer (39, n=l) in the cyclohexenyl case can be explained by the isomerization of the initial adduct (44), which can not cyclize due to ring-strain, to the other 7t-allyl-Pd intermediate (45) which then ring-closes to (39) (Scheme 2.13) [20]. While the yields may not be spectacular, it is still remarkable that these reactions proceeded as well as they did since the substrates do contain another allylic ester moiety which is known to undergo ionization in the presence of the same palladium catalyst. 

Whereas the utility of these methods has been amply documented, they are limited in the structures they can provide because of their dependence on the diazoacetate functionality and its unique chemical properties. Transfer of a simple, unsubstituted methylene would allow access to a more general subset of chiral cyclopropanes. However, attempts to utilize simple diazo compounds, such as diazomethane, have never approached the high selectivities observed with the related diazoacetates (Scheme 3.2) [4]. Traditional strategies involving rhodium [3a,c], copper [ 3b, 5] and palladium have yet to provide a solution to this synthetic problem. The most promising results to date involve the use of zinc carbenoids albeit with selectivities less than those obtained using the diazoacetates. 

A variant on this structure, dioxyline, has much the same activity as the natural product but shows a better therapeutic ratio. Reduction of the oxime (113) from 3,4-dimethoxyphenyl-acetone (112) affords the veratrylamine homolog bearing a methyl group on the amine carbon atom (114). Acylation of this with 4-ethoxy-3-methoxyphenyl acetyl chloride gives the corresponding amide (115). Cyclization by means of phosphorus oxychloride followed by dehydrogenation over palladium yields dioxyline (116). ... 

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