Arylation using silver salts

The first example of the intermolecular AHR was reported by Hayashi et al. and involved the asymmetric arylation of 2,3-dihydrofurans using aryl triflates [18]. Although little or no enantiomeric excess was obtained when aryl iodide/silver salt combinations were used, the use of triflates along with the familiar Pd(OAc)2/ BINAP catalyst system resulted in the formation of the 2-aryl-2,3-dihydrofuran product 54, together with minor amounts of the 2, 5-dihydrofuran isomer 55. The rationale proposed by the authors for this outcome is shown in Scheme 12 it is hypothesized that addition of the catalytic complex to either face of the sub-... 

Based on studies directed towards chelation-assisted oxidative homocouplings of 2-arylpyridines, a protocol was developed for intermolecular coupling reactions [132]. Thus, benzo h quinoline (186) was efficiently arylated with a variety of arenes using silver salts and benzoquinone as additives (Scheme 9.53). 

Tamaru and coworkers [9] have reported an alternative method of realizing a selective Hy-abstraction without using silver salts. Allylic carbamates 8 can be transformed into the corresponding cinnamyl derivatives 10 by the Mizoroki-Heck arylation with iodobenzene (Figure 7.6). A six-membered chelate intermediate 9 has been proposed for the selective Hy-abstraction. 

A number of modified reaction conditions have been developed. One involves addition of silver salts, which activate the halide toward displacement.94 Use of sodium bicarbonate or sodium carbonate in the presence of a phase-transfer catalyst permits especially mild conditions to be used for many systems.95 Tetraalkylammonium salts often accelerate reaction.96 Solid-phase catalysts in which the palladium is complexed by polymer-bound phosphine groups have also been developed.97 Aryl chlorides are not very reactive under normal Heck reaction conditions, but reaction can be achieved by inclusion of triphenylphosphonium salts with Pd(OAc)2 or PdCl2 as the catalyst.98... 

Trimethylsilyl groups also may be lost from vinylic or allylic positions in the arylation reaction.70 Halide ion facilitates die desilylation as well as the loss of alkoxy and acetoxy groups. Inclusion of soluble silver salts in reactions where trimethylsilyl groups are lost prevents this reaction.70 The reaction in the absence of silver ion is useful for preparing styrene derivatives. However, they also may be prepared directly from aryl halides and ethylene in fair to good yields.71... 

Pale and coworkers provided the first example of combined desilylation/coupling catalytic for silver. They found that 1-trimethylsilyl-l-alkynes in the presence of tetrakis(triphenylphosphine)palladium, a silver(I) salt, and an activator (potassium carbonate in methanol, or TBAF-3H20) in DMF coupled with vinyl triflates and aryl iodides to give enynes good yields (Scheme 1.66).143,144 Although silver salt was not necessary for reaction when TBAF-3H20 was used for activation of the carbon-silicon bond, a small to significant improvement was observed for all reported... 

The classical Hunsdiecker reaction (equation 18), involving the reaction of silver caiboxylates widi halogens, and the various associated side reactions, has been reviewed several tunes. Optimum yields are obtain widi bromine, followed by chlorine. Iodine gives acceptable yields provid diat the correct stoichiometry of 1 1 is used. The reaction is most frequently carried out in tetrachloromediane at reflux. From a practical pmnt of view, one drawback is the difficulty encountered in the preparation of dry silver caiboxylates the reaction of silver oxide on the acyl chloride in tetrachloromediane at reflux has been employed to circumvent diis problem. Evidendy the use of molecular bromine limits die range of functional groups compatible widi die reaction the different reaction pathways followed by the silver salts of electron poor (equation 19) and electron rich (equation 20) aryl carboxyl s illustrate this point well. 

The triarylaminium salts [N(aryl)3][X] in which the para position is substituted (in order to inhibit nucleophilic reactions at that position) are among the most useful oxidants because they are strong, almost innocent oxidants known for a range of standard redox potentials from 0.16 V to -1.76 V relative to FeCp2 depending of the nature and number of substituents (Table 10), and they are easily accessible by oxidation of the triarylamine in CH2CI2 using [NO] salts, silver salts in the presence... 

Jododesilylation. Arylsilanes can be used as surrogates of aryl iodides by virtue of this facile conversion. A silver salt may or may not be required to facilitate the reaction. 

One of the most general approaches to the synthesis of this type of compounds involves the Lewis acid promoted rearrangement of acetals of a-substituted propiophenones [4,5]. Besides silver salts, a large variety of soft and borderline Lewis acids have been found to be convenient catalysts for the 1,2-aryl shift, noticeably zinc halides in substoichiometric amounts [6]. As final products need to be free of metal traces for human consume, the use of Lewis acids supported on microporous solids can be advantageous since a better recovering of the catalyst can be anticipated. 

One particular radical decarboxylation reaction, which is used in the synthesis of alkyl or aryl bromide (Hunsdiecker reaction), involves reaction of the silver salt of a carboxylic acid with bromine, and results overall in loss of CO2 to form the corresponding alkyl or aryl bromide (Scheme 4.47). When silver carboxylate is treated with I2 ester formation occurs (Simonini reaction). 

Furthermore, addition of tetra-n-butylammonium chloride improved the selectivity in certain reactions, such as in the arylation of allylic alcohols.Finally, an appropriate selection of tetraalkylammonium salt-based systems can be used to control the product pattern in certain Heck reactions (Scheme 34). In these examples, phase transfer agents have been shown to be an alternative to silver salts in directing the outcome of the reaction.t t " ... 

Jeffery has reported an alternative additive-based solution to yield Hy-abstracted products. Mizoroki-Heck reaction of allylic alcohols with aryl or alkenyl hahdes in the presence of silver salts (AgOAc or Ag2C03) results in selective Hy -abstraction [7]. Similar hydroxy-coordination to the cationic organopalladium intermediates are believed to be involved in this system. In this regard, the use of hypervalent iodonium salts is also effective for generating cationic palladium species [8]. 

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