Aryl halides dehalogenation

Ni(Gl)Gp(carbene) complexes with the carbenes l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro imidazol-2-ylidene, l,3-bis(2,6-diisopropylphenyl)-4,5-dihydorimidazol-2-ylidene, and l,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene have also been prepared, structurally characterized, and shown to have catalytic activities in the aryl amination and aryl halide dehalogenation reactions. Structurally similar carbene complexes have also been reported with the novel carbene formed by aryl cyclohexadienyl-ylidene rearrangement, as shown in Equation (11) the solid-state structure of this complex has shown an Ni-Gcarben bond of ca. 189 pm. 

Formate is an excellent hydride source for the hydrogenolysis of aryl halides[682]. Ammonium or triethylammonium formate[683] and sodium formate are mostly used[684,685]. Dechlorination of the chloroarene 806 is carried out with ammonium formate using Pd charcoal as a catalyst[686]. By the treatment of 2,4,6-trichloroamline with formate, the chlorine atom at the /iiara-position is preferentially removed[687]. The dehalogenation of 2,4-diha-loestrogene is achieved with formic acid, KI, and ascorbic acid[688]. 

In the presence of a precious metal catalyst, aryl halides can undergo dehalo-dimerization to give biaryl products, with varying degrees of selectivity. The major byproduct of this reaction is usually the dehalogenated aryl compound. This type of chemistry is currently one of the very few viable means for the large scale preparation of biaryl compounds. 

Aryl halides can be dehalogenated by Friedel-Crafts catalysts. Iodine is the most easily cleaved. Dechlorination is seldom performed and defluorination apparently never. The reaction is most successful when a reducing agent, say, Br or 1 is present to combine with the I" or Br coming off." Except for deiodination, the reaction is seldom used for preparative purposes. Migration of halogen is also found," both intramolecular and intermolecular." The mechanism is probably the reverse of that of 11-11." ... 

The present reaction may be reasonably explained by the smooth oxidative addition of aryl halides to metallic nickel to give aryl nickel halides, followed by disproportionation to bisarylnickels, which upon reductive elimination afford the dehalogenative coupled products. Providing strong support for this mechanism, the intermediates, arylnickel halide and bisarylnickel (Ar=C F ), were isolated as the phosphine complexes. 

In contrast to [L Pd], oxidative addition of aryl halides on [L Ni] often proceed by single electron transfer mechanism [2, 197]. SN2 and SNAr types of oxidative addition as a step of the catalytic dehalogenation have also been proposed in the literature for low-valent Ti [40, 114], Zr(II) [115], Ru(II) [20, 74, 81, 98],... 

FIGURE 4.65 Mechanism of oxidative dehalogenation of an aryl halide. 

Several factors govern the transport and fate of hydrophobic organic chemicals in sediment/water environments microbially mediated reactions and sorption are major processes affecting the fate of these compounds in aquatic systems [166,366-368]. Aryl halides have been shown to undergo microbially-mediated dehalogenation under anaerobic conditions [38, 52, 68, 105, 116,... 

Aryl halides can be dehalogenated with triethylsilane in the presence of a palladium catalyst. The method is versatile and can also be used for the reduction of acyl chlorides to aldehydes, or benzylicbromides to the corresponding hydrocarbons. If different types of halides are present in the molecule, selective dehalogenation takes place. Thus, an aryl iodide can be reduced in the presence of a chloride, and benzylic bromide is reduced more easily than an aryl bromide. Finally, the method is even able to distinguish between two aryl bromides in the same molecule (Scheme 4.41)67. 

Lithium triethylborohydride (Super-Hydride) is a much more powerful reducing agent than lithium aluminium hydride. It is useful for the reductive dehalogenation of alkyl halides, but unlike lithium aluminium hydride does not affect aryl halides. It is available as solution in tetrahydrofuran in sealed containers under nitrogen. The solutions are flammable and moisture sensitive and should be handled with the same precautions as are taken with other organometallic reagents (see Section 4.2.47, p. 442). 

The mild reaction conditions allow the preparation of boronates which are not accessible via lithium or Grignard intermediates followed by borylation. The use of HBPin instead of B2Pin2 allows similar reactions in large scale synthesis, and also tolerates various reducible functional groups, although side products may arise due to dehalogenation of the aryl halide. 

A variety of other alkyl and aryl halides were successfully dehalogenated by polymer-supported organotin hydrides even in the presence of functional groups155,157,160,168,169,181,188. Two representative examples are shown in Scheme 39. 

In 2007 the scope of the trialkylborane/water system was extended to the dehalogenation of alkyl iodides and the chemoselective deoxygenation of secondary alcohols in the presence of alkyl and aryl halides [86]. The rate constants for the hydrogen-atom transfer from this reagent to secondary radicals (Scheme 37) are substantially lower than those of the Ti(III) aqua-complex [78, 87]. 

In the presence of electron donors, photodechlorination of chlorobenzene390, 4-chloroanisole378 and other aryl halides is enhanced. The key step in this process is electron transfer from the donor to the excited halide. A kinetic study, based on determination of quantum yields and fluorescence quenching efficiencies, has revealed that in the triethyl-amine-assisted dehalogenation of chlorobenzene the product-forming interaction occurs with the triplet excited state (equations 97-99)390. 

The factors affecting the relative reactivity of aryl halides in SrnI reactions have been analysed and compared645. Competition experiments of pairs of substrates, in photo-stimulated reactions with pinacolone enolate ion in liquid ammonia, reveal a spread of reactivity exceeding three powers of ten. The ease of formation of the radical anion of the substrate appears to dominate the overall reactivity. The rate of dehalogenation of the radical anion may become important when its stability exceeds a certain threshold. When the fragmentation rate of the radical anion intermediate is fairly slow, the overall reactivity diminishes. 

Scheme 20 Proposed mechanism for dehalogenation of aryl halides...

Oxidative addition of C2 - H bonds of imidazolium salts to low valent metals was first observed by Nolan and coworkers in 2001, who proposed a NHC - Pd - H intermediate in the catalytic cycle of the dehalogenation of aryl halides with Pd(dba)2 in the presence of imidazolium salts [154]. More direct evidence of this process was described by Crabtree and coworkers two years later [155]. The reaction between a pyridine-imidazolium salt and Pd2(dba)3 afforded the preparation of bis-NHC - Pd(II) complexes by C2 - H oxidative addition (Scheme 40). The presumed Pd - H intermediates were not detected. The authors proposed a mechanism via two successive C - H oxidative additions followed by reductive elimination of H2 [ 155]. 

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