Correlations palladium substitution reactions

This trend is also observed in palladium chemistry where the general order for oxidative addition often correlates with that of nucleophilic substitution. Not only are 2-, 4- and 6-chloropyrimidines viable substrates for Pd-catalyzed reactions, but 4- and 6-chloropyrimidines react more readily than 2-chloropyrimidines. 

In the process of olefin insertion, also known as carbometalation, the 1,2 migratory insertion of the coordinated carbon-carbon multiple bond into the metal-carbon bond results in the formation of a metal-alkyl or metal-alkenyl complex. The reaction, in which the bond order of the inserted C-C bond is decreased by one unit, proceeds stereoselectively ( -addition) and usually also regioselectively (the more bulky metal is preferentially attached to the less substituted carbon atom. The willingness of alkenes and alkynes to undergo carbometalation is usually in correlation with the ease of their coordination to the metal centre. In the process of insertion a vacant coordination site is also produced on the metal, where further reagents might be attached. Of the metals covered in this book palladium is by far the most frequently utilized in such transformations. 

We recently studied if it is possible to device a selection strategy based on the relative stability of the intermediate of a reaction [24]. It is known that in the palladium-catalyzed allylic substitution, the rate-determining step is the attack of the nucleophile on the n-allyl-palladium species. The transition state of this step is believed to be late when carbon nucleophiles are used. In this scenario, an inverse correlation of the energy of the intermediate and the reaction rate is expected, as the transition state is more product-like (see Figure 4.10). Based on this hypothesis, the selection of catalyst among a dynamic mixture of palladium complexes was studied. 

Substitution. The kinetics of reactions of /ra/t -CPdClgCR SR ) ] complexes with a series of amines of various basicities and steric requirements have been studied in 1,2-dimethoxyethane at 298 K. In fact the first step is fast, and it is the second step whose kinetics have been examined here. Amine basicity is an important factor logarithms of second-order rate constants correlate linearly with amine pKa values in the absence of steric hindrance. Steric factors have a large effect when the incoming amine e.g. 2-methylpyridine) or the leaving sulphide (e.g. phenyl isopropyl sulphide) is bulky. The kinetic pattern for the reaction of [PdCl2(cod)] with 2,2 -bipyridyl in aqueous methanol has been interpreted by the reaction sequence shown in Scheme 3. The mechanism is dissociative with respect to the palladium centre. The rate law for the reaction of the [PdBr(dien)]+ cation with inosine has already been discussed in the introductory section to this chapter. 

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