Pd2

Attention should be paid to the fact that the ratio of Pd and phosphine ligand in active catalysts is crucial for determining the reaction paths. It is believed that dba is displaced completely with phosphines when Pd2(dba)3 is mixed with phosphines in solution. However the displacement is not eom-plcte[16]. Also, it should be considered that dba itself is a monodentate alkene ligand, and it may inhibit the coordination of a sterically hindered olefinic bond in substrates. In such a case, no reaction takes place, and it is recommended to prepare Pd(0) catalysts by the reaction of Pd(OAc)2 with a definite amount of phosphinesflO]. In this way a coordinatively unsaturated Pd(0) catalyst can be generated. Preparation of Pd3(tbaa)3 tbaa == tribenzylidene-acetylacetone) was reported[17], but the complex actually obtained was Pd(dba)2[l8],... 

Reactions of Organic Halides and Pseudo-Halides. COjMe Pd2(dba)], (o-toOaP... 

The diazonium salts 145 are another source of arylpalladium com-plexes[114]. They are the most reactive source of arylpalladium species and the reaction can be carried out at room temperature. In addition, they can be used for alkene insertion in the absence of a phosphine ligand using Pd2(dba)3 as a catalyst. This reaction consists of the indirect substitution reaction of an aromatic nitro group with an alkene. The use of diazonium salts is more convenient and synthetically useful than the use of aryl halides, because many aryl halides are prepared from diazonium salts. Diazotization of the aniline derivative 146 in aqueous solution and subsequent insertion of acrylate catalyzed by Pd(OAc)2 by the addition of MeOH are carried out as a one-pot reaction, affording the cinnamate 147 in good yield[115]. The A-nitroso-jV-arylacetamide 148 is prepared from acetanilides and used as another precursor of arylpalladium intermediate. It is more reactive than aryl iodides and bromides and reacts with alkenes at 40 °C without addition of a phosphine ligandfl 16]. 

Fn some cases, r-allylpalladium complex formation by retention syn attack) has been observed. The reaction of the cyclic allyiic chloride 33 with Pd(0) affords the 7r-allylpalladium chlorides 34 and 35 by retention or inversion depending on the solvents and Pd species. For example, retention is observed in benzene, THF, or dichloromethane with Pd2(dba)3. However, the complex formation proceeds by inversion in these solvents with Pd(Ph3P)4, whereas in MeCN and DMSO it is always inversion[33]. The syn attack in this case may be due to coordination of Pd to chlorine in 33, because Pd is halophilic. The definite syn attack in complex formation has been observed using stereoche-mically biased substrates. The reaction of the cxoallylic diphenylphosphino-acetate 36 with phenylzinc proceeds smoothly to give 37. The reaction can be explained by complex formation by a syn mechanism[31]. However, these syn attacks are exceptional, and normally anti attack dominates. 

BU3P. A rapid redox reaction takes place to yield the active Pd(0) species and tributylphosphine oxide. The Pd(0) thus generated is a phosphine-free cata-lyst[341]. Severe reaction conditions are necessary, or no reaction takes place, when Pd2(dba)3 is used in the elimination reaction of cyclic allylic compounds with an excess of -Bu3P[342]. 

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