Cross coupling reactions benzoyl chlorides

Cyclic triarylbismuth(III) compounds also undergo the Pd-catalyzed cross-coupling reaction with benzoyl chloride (Scheme 27) [42]. The exocyclic aryl group was selectively transferred to form 4-methylbenzophenone in good yield. Bismuth-containing products could not be isolated except for the cyclic bismuth compound possessing a SO2 moiety, for which cyclic bismuth chloride was isolated in 86% yield. 

Scheme 27 Cross-coupling reaction of cyclic triarylbismuth compounds with benzoyl chloride...

By contrast, for iodide 18 having the triple bond activated by a phenyl group, conversion to the cyclic organozinc species 25 occurred effectively and the latter could be efficiently functionalized, provided that traces of moisture were excluded by pre-treatment of zinc powder with Mel. The substituted benzylidene cyclopentanes 26 and 27 were respectively obtained after iodinolysis and palladium-catalyzed cross-coupling reaction with benzoyl chloride (equation 10). However, it could not be assessed whether the formation of organozinc 25 was attributable to an anionic or a radical cyclization pathway (or both) as, had iodide 26 been produced by a radical iodine atom-transfer, it would have been converted to 25 by reaction with metallic zinc due to the presence of the activating phenyl group21. 

Scheme 16 shows parallel syntheses of cyclic and acyclic amide compounds. Fluorous benzaldehydes were first subjected to reductive amination reactions. The resulting amines were then reacted with isocyanates to form substituted hydantoin rings 14 or with benzoyl chlorides to form amides 15. Purified F-sulfonates were used for palladium-catalyzed cross-coupling reactions to form corresponding biaryl 16 [31] and arylsulfide 17 [32] products, respectively. 

An interesting feature of the reaction of organozinc compounds is shown in Scheme 4. Reaction of /3-iodozinc derivative 1 with benzoyl chloride in the presence of Pd[P(o-tol)3l4 catalyst gave the iyn-isomer 2, while the anti-isomer 3 was produced by reaction of 1 with benzaldehyde followed by oxidation. The nucleophilic addition to the aldehyde occurs via inversion of the configurations in contrast to the Pd-catalyzed cross-coupling reaction, which proceeds via retention of the configurations. 

Table 5.11 Reaction of copper anion with organohalides and subsequent cross-coupling reactions with benzoyl chloride.

Unfortunately, no oxidative addition was found to occur with phenyl tosylate even at refluxing temperatures (Table 8.12, entry 9). The formation of organomanganese tosylates was also confirmed by the subsequent cross-coupling reaction with different electrophiles. The tosylates listed in Table 8.12 reacted with benzoyl chloride to afford the corresponding ketones in moderate to excellent yields (44-86%). Once again, the coupling reaction vras carried out at... 

Table 9.2 Cross-coupling reactions of calcium organocuprate reagents with benzoyl chloride.°...

Reactions of Pyrroles. 1,3-Di-t-butylpyrrole forms the first stable protonated pyrrole, the salt (104). Electrophilic substitution of pyrrole with MeaC or Me FC in the gas phase occurs mainly at the j3-position, as does nitration and Friedel-Crafts acylation of l-phenylsulphonylpyrrole2 Pyrrole-2,5-dialdehyde has been prepared by Vilsmeier-Haack formylation of the ester (105), followed by hydrolysis. A similar method has been used to convert the di-acetal (106) into pyrrole-2,3,5-tricarbaldehyde. AT-Benzoyl-pyrrole reacts with benzene in the presence of palladium(II) acetate to yield a mixture of l-benzoyl-2,5-diphenylpyrrole, the bipyrrolyl (107), and compound (108). Treating lithiated A-methylpyrrole with nickel(II) chloride results in the polypyrrolyls (109 = 0-4). 2-Aryl-1-methylpyrroles are obtained by cross-coupling of l-methylpyrrol-2-ylmagnesium bromide with aryl halides in the presence of palladium(0)-phosphine complexes. ... 

Preparation of Heteroarylmanganese Reagents and Their Cross-Coupling Chemistry 357 Table 8.26 Reactions of heteroaryl manganese bromides with benzoyl chloride. 

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