Palladium-catalyzed carbonylative coupling

When the homocoupling reaction is performed in the presence of carbon monoxide, the palladium-catalyzed carbonylative coupling of organolead compounds takes place (Equation (104)). Thus, organolead triacetates can be carbonylated in the presence of Pd2(dba)3, CHC13 (5 mol%) and NaOMe (5 equiv.) in acetonitrile under atmospheric pressure of carbon monoxide at room temperature to afford good yields of the symmetrical ketones.118... 

In 1979 the reaction of benzyl and aryl halides was reported with mechanistic discussions [8, 9]. The first palladium-catalyzed carbonylative coupling of organic halides with organotin compounds was reported by Tanaka in the same year (Scheme 4) [10,11]. 

Ma W, Li X, Yang J, Liu Z, Chen B, Pan X (2006) A convenient synthesis of aryl ferrocenylethynyl ketones and 2-ferrocenyl-4H-chromen-4-ones via palladium-catalyzed carbonylation coupling. Synthesis 2489-2492... 

The construction of -silyl divinyl ketones in many different structural settings has been weU developed. The four principal connections outlined in Scheme 16 are as follows path a, vinyl organome-tallic addition to 3-trimeAylsilyl-2-propenal path b, 3-trialkylsilylvinyl organometallic" addition to enals path c, palladium-catalyzed carbonylation/coupling of 2-trimethylsilylvinyltrimethylstan-nane and path d, acylation of a B-silyl copper reagent. 

The palladium-catalyzed carbonylative coupling reaction of alkenyl halides with organoboron compounds in the presence of carbon monoxide is a valuable procedure for the synthesis of unsymmetrical ketones. " ... 

In the laboratory of L.S. Hegedus, the total synthesis of (+)-ep/-jatrophone was accomplished using a palladium-catalyzed carbonylative coupling as the key step. In the endgame of the synthesis, a 3-hydroxy ketone moiety was oxidized in excellent yield to the corresponding 1,3-dione using the mild Corey-Kim protocol. 

Gyorkos, A. C., Stille, J. K., Hegedus, L. S. The total synthesis of ( )-epi-jatrophone and ( )-jatrophone using palladium-catalyzed carbonylative coupling of vinyl triflates with vinyl stannanes as the macrocycle-forming step. J. Am. Chem. Soc. 1990,112, 8465-8472. 

Kiji, J., Okano, T., Kimura, H., Saiki, K. Palladium-catalyzed carbonylative coupling of iodobenzene and 2-methyl-3-butyn-2-ol under biphasic conditions Formation of furanones. J. Mol. Catal. A Chemical 1998,130, 95-100. 

Wu, X.-F., Neumann, H., Beller, M. Palladium-catalyzed carbonylative coupling reactions between Ar-X and carbon nucleophiles. Chem. Soc. Rev. 40, 4986 (2011)... 

In 1993 Suzuki and colleagues described the palladium-catalyzed carbonylative coupling of aryl iodides with aryl boronic acids [13]. Various diarylketones were produced in high yields (Scheme 4.4). The choice of base and solvent was essential to obtain the desired ketones without biaryl by-products. The coupling of benzyl bromide was also described. In 1998 the group extended this methodology to aryl bromides and triflates [14]. In the case of aryl bromides, Nal or KI was required as an additive. The in situ transformation of aryl bromides to aryl iodides may be involved. 

The palladium-catalyzed carbonylative coupling of aryl diazonium ions with aryl boronic acids was published in 2002 [24]. Various aryl ketones were produced in moderate to high yields under mild conditions (Scheme 4.10). The benefit of... 

Palladium-catalyzed carbonylative couplings of iodoferrocene with arylboronic acids were reported by Yang and colleagues [32]. A series of aryl ferrocenyl ketones was prepared in good yields under mild conditions (Scheme 4.16). Both strongly activated and ortho-substituted arylboronic acids gave the corresponding ketones in moderate yields. 

Gennari and his group reported a more sophisticated palladium-catalyzed carbonylative coupling of vinyl stannanes with electron-poor enol triflates [61]. The effect of ligands and additives was tested, and a combination of Pd2dba3, AsPh3, LiCl, Cul and NMP proved to be the optimal system. Later, this methodology was applied to the total synthesis of sarcodictyins [62]. 

In 2001 Yun and colleagues used a solid-supported organostannane, which was reacted with aryl halides in a palladium-catalyzed carbonylative coupling reaction [63] to produce a wide range of diaryl ketones. 

Mann et al. showed that various acetophenones can be synthesized by carbonylative coupling of aryl triflates with SnMe4 [65]. Under mild conditions using the catalyst system Pd(OAc)2/dppp, good yields (70-94 %) were obtained (Scheme 4.32). In 2002 Mido and colleagues reported the palladium-catalyzed carbonylative coupling of tributyl(l-fluorovinyl)stannane with aryl halides and aryl triflates [66]. In the presence of a catalytic amount of palladium catalyst and CsF in DMF, aryl 1-fluorovinyl ketones were formed in good yields. 

More recently, Morken and colleagues described a rare example of using unsaturated carbonyls for palladium-catalyzed carbonylative coupling reactions with dialkylzinc reagents [81]. 1,4-Diketones were synthesized in good yields... 

More recently, Lee and Park described a palladium-catalyzed carbonylative coupling of aryl iodides with trimethylsilylacetonitrile to benzoylacetonitriles (Scheme 4.48) [87]. A high functional group tolerance was observed, and no additional ligands were needed. 

Scheme 4.48 Palladium-catalyzed carbonylative coupling of aryl iodides and trimethylsilylacetonitrile...

In 2012, Grushin s team developed a palladium-catalyzed carbonylative coupling of aryl iodides with sodium azide [103]. This catalytic reaction occurs smoothly at temperatures as low as 25-50 °C and 1 bar to cleanly produce aroyl azides from the corresponding aryl iodides, CO and NaNs (Scheme 4.52). The reaction exhibits high-functional group tolerance and can also be conveniently used for one-pot, two-step procedures furnishing primary benzamides, imino-phosphoranes, isocyanates, and ureas in high yield without isolation of the primary benzoyl azide product. 

Above we mentioned the palladium-catalyzed carbonylative coupling of organohalides with C-H nucleophiles. Compared with their version of carbonylative coupling with organometaUic reagents, the pre-activation of C-H bonds was not needed. The other pathway in carbonylative C-H activation is the reaction between two nucleophiles in the presence of an additional oxidant sometimes these types of reactions are also called oxidative carbonylations. Only the reaction between Ar-H and nucleophiles will be discussed in the following the other oxidative carbonylation reactions will be summarized in Chap. 8. 

In 2002 Ryu and colleagues reported on similar work that was catalyzed by Pd in the presence of light [19]. Similar products are obtained by the palladium-catalyzed carbonylative coupling of allyl acetate with benzynes [20]. 

Similar to their previous work, Alper and colleagues succeeded in describing a palladium-catalyzed carbonylative coupling of o-iodoanihnes with allenes in 2007 [27]. Quinolinones were synthesized in moderate to good yields under low CO pressure (5 bar) (Scheme 7.8). Here, an ionic liquid was used as solvent and promoter to enhance the efficacy of the cyclization protocol. Interestingly, the recyclability of the system was also demonstrated. 

Scheme 7.7 Palladium-catalyzed carbonylative coupling of o-iodophenols with allenes...

Strychnine was first isolated in 1818 from Strychnos ignatii by Pelletier and Caventou. Overman and colleagues did the first asymmetric total synthesis of strychnine [51]. A palladium-catalyzed carbonylative coupling of aryl iodide with an organostannanes reagent was used for the preparation of one of the intermediates (Scheme 10.6). The entire synthesis was accomplished in 20 steps and... 

The methodology was applied to total synthesis of natural products [90]. The presence of a doubly unsaturated ketone in anatural products of the eleustide family, suggested the application of the palladium-catalyzed carbonylative coupling between the electron-poor (carboalkoxy-substituted) unsaturated triflate 52... 

Crisp, G.T., Scott, W.J. and Stille, J.K. (1984) Palladium-catalyzed carbonylative coupling of vinyl triflates with organostarmanes. A total synthesis of ( )A American Chemical Society, 106, 7500-7506. 

Ciattini, P.G., Morera, E., Ortar, G. and Rossi, S.S. (1991) Preparative and regiochemical aspects of the palladium-catalyzed carbonylative coupling of 2-hydroxyaryl iodides with efhynylarenes. Tetrahedron, 47, 6449-6456. 

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