REACTION OF ARYL HALIDES WITH

Aryl sulfides are prepared by the reaction of aryl halides with thiols and thiophenol in DMSO[675,676] or by the use of phase-transfer catalysis[677]. The alkenyl sulfide 803 is obtained by the reaction of lithium phenyl sulfide (802) with an alkenyl bromide[678]. 

Benzyne is formed as a reactive intermediate in the reaction of aryl halides with very strong bases such as potassium amide... 

The Phillips approach involved the reaction of aryl halides with aromatic nuclei in the presence of Friedel-Crafts catalysts. Whilst many variations in the process existed three main cases were distinguishable. 

Coupling Reactions of Aryl Halides with Ketones and Amines19,20 56... 

Ketones, coupling reactions of aryl halides with, 487-489 k-factor, 244 Kinetic studies, 73 Kumada coupling, 467, 489, 491... 

Examples of the intermolecular C-P bond formation by means of radical phosphonation and phosphination have been achieved by reaction of aryl halides with trialkyl phosphites and chlorodiphenylphosphine, respectively, in the presence of (TMSlsSiH under standard radical conditions. The phosphonation reaction (Reaction 71) worked well either under UV irradiation at room temperature or in refluxing toluene. The radical phosphina-tion (Reaction 72) required pyridine in boiling benzene for 20 h. Phosphinated products were handled as phosphine sulfides. Scheme 15 shows the reaction mechanism for the phosphination procedure that involves in situ formation of tetraphenylbiphosphine. This approach has also been extended to the phosphination of alkyl halides and sequential radical cyclization/phosphination reaction. ... 

The generated palladium chlorides possessing phosphinous acid ligands were found to be remarkably active and efficient catalysts in the presence of bases for a variety of cross-coupling reactions of aryl halides with aiylboronic... 

Reaction of allyl nalides with the iron powders is rapid and exothermic and leads to near quantitative yields of the self-coupled product 1,5-hexadiene. Similarly, reaction of benzyl chloride with the iron powders at room temperature yields bibenzyl in 60-70% yields along with 20-25% of toluene. In contrast, reaction of aryl halides with the iron powders leads to reductive cleavage rather than self-coupling. Similarly, reaction of 1-bromoheptane with the iron powder in THF for three hours at room... 

The intermolecular coupling of lactams and acyclic amides has also been reported. Reactions of carbamates with aryl halides occurred in the presence of catalysts ligated by P(/-Bu)3.78 Both carbamates and amides coupled with aryl halides in the presence of a catalyst bearing Xantphos.90 In addition, the coupling of lactams with aryl halides has been successful. A combination of Pd(OAc)2 and DPPF first formed A-aryl lactams in good yields from 7-lactams, but the arylation of amides was improved significantly by the use of Xantphos (Equations (20) and (21)).90 91 The reaction of aryl halides with vinyligous amides has also been reported 92... 

Reactions of aryl halides with phenoxides or phenols (Equation (30)) and base catalyzed by complexes of these ligands occurred in significantly higher yields than did the same reactions catalyzed by complexes of DPPF or BINAP. For example, a large number of diaryl ethers have... 

The photoinduced reactions of aryl halides with the thiourea anion afford arene thiolate ions in DMSO. These species can be used without isolation for... 

The earliest developments in transition metal-assisted formation of aromatic C-P linkages were the result of the efforts of Tavs28 that were concerned with the use of Ni(II) halide salts for the reaction of aryl halides with trialkyl phosphites. These reactions involved conditions reminiscent of the Michaelis-Arbuzov reaction (heating at an elevated temperature) and produced arylphosphonate products in reasonable yield (Figure 6.8). 

Similarly, copper salts (cupric and cuprous) facilitate the reaction of aryl halides with trialkyl phosphites in the formation of dialkyl arylphosphonates under conditions like those found in nickel systems.37-39 Again, the copper salts appear to undergo an initial reaction with the phosphites to form a complex that subsequently undergoes reaction with the aryl halide. The requirement for copper is also similar to that for nickel saltstonly a catalytic amount is needed. Further, a preference among halides on the aromatic ring is noted iodide is replaced preferentially to other halides (Figure 6.10).40... 

Arylation of C-H bonds is achieved by coupling reactions of C-H bonds with aromatic compounds such as halides, triflates, and organometallic reagents. Early works in this field involve the reaction of aryl halides with norbornene. As shown in Scheme 5, the coupling reaction of bromobenzene with norbornene in the presence of Pd(PPh3)4 as a... 

Among early reported Pd-catalyzed reactions, the Mori-Ban indole synthesis has proven to be very useful for pyrrole annulation. In 1977, based on their success of nickel-catalyzed indole synthesis from 2-chloro-fV-allylaniline, the group led by Mori and Ban disclosed Pd-catalyzed intramolecular reactions of aryl halides with pendant olefins [122]. Compound 102, easily prepared from 2-bromo-lV-acetylaniline and methyl bromocrotonate, was adopted as the cyclization precursor. Treatment of 102 with Pd(OAc)2 (2 mol%), Ph3P (4 mol%) and NaHCQ3... 

Raney nickel alloy, reduction of aromatic nitriles to aldehydes, 51, 22 REACTION OF ARYL HALIDES WITH... 

Reactions of aryl halides with the reactive calcium required slightly higher temperatures, up to -30°C for aryl bromides and up to -20°C for aryl chlorides.1 2 3 4 5 Surprisingly, the active calcium reacted readily with fluorobenzene at room temperature to form the corresponding organocalcium reagent in near quantitative yield. 

Palladium-catalyzed reaction of aryl halides with diboron reagent to produce aryl-boronates. Also known as Hosomi-Miyaura borylation. 

REACTION OF ARYL HALIDES WITH Tt-ALLYLNICKEL HALIDES METHALLYLBENZENE... 

Amines are generally prepared by nucleophilic amination, which is a coupling of carbon electrophiles with a nucleophilic amination reagent, NR2, and Ni and Pd catalyzed reaction of aryl halides with arylamines (Hartwig-Buchwald amination) . Thus, the direct C—N bond formation between carbon nucleophiles and electrophilic nitrogen functionality R2N+ constitutes an example of the umpolung methodology. 

Although the preparation has been repeated, there have been no other reports of the type of reaction, (described in 1923) in which carbazole in the presence of excess potassium hydroxide and nitrobenzene at only 50°C gave a good yield of 9-(4-nitrophenyl)-carbazole, presumably via an adduct such as 43 subsequently oxidized by excess nitrobenzene and/or air. More recent examples of N-arylation of carbazoles have involved copper catalysis in reaction of aryl halides with carbazoles. Thus, copper bronze and potassium carbonate heated with the carbazole and the appropriate aromatic halide have produced 9-(4-methoxyphenyl)- and 9-(2-tolyl)carbazoles 9-(4-phenylphenyl)carbazole, l,4-di(carbazol-9-yl)benzene, 4,4 -di(carbazol-9-yl)biphenyl, and 9-(2-pyridyl)- and 9-(2-quinolyl)carbazoles 9-[2-(2-phenylphenyl)phenyl]- and 9-[2-(4-methylphenyl)phenyl] carbazoles 9-(3-bromo-6-nitrophenyl)-, 9-[3-(carbazol-9-yl]-, 9-(2-nitrophenyl)-, 9-(4-methyl-2-nitrophenyl)-, 9-(4-methoxycarbonyl)-l-nitro-, and l-nitro-9-(4-tolyl)carbazoles 9-(2-methoxycarbonylphenyl)carbazole 9-[2- 2-... 

Cross-coupling reaction of aryl halides with arylamines is a straightforward method for forming a carbon-nitrogen bond and is catalyzed by a palladium complex. This methodology was applied by Kanbara, Mullen, and several groups to... 

Carbonylation of halides with tetramethyltin This nickel complex is the most efficient catalyst for the synthesis of methyl ketones by reaction of aryl halides with carbon monoxide and tetramethyltin in HMPT at 120°. No reaction occurs when tetraphenyltin is used. A typical reaction is formulated in equation (I). 

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