Suzuki-Miyaura reaction/cross-coupling

Chamoin S, Houldsworth S, Kruse CG, Bakker WI, Snieckus V. The Suzuki-Miyaura cross coupling reactions on solid support. Link to solution phase directed ortho metalation. The Leznoff acetal linker approach to biaryl and heterobiaryl aldehydes. Tetrahedron Lett 1998 39 4179-4182. 

Using a conventional dorm-room quality microwave oven, we have successfully performed Suzuki-Miyaura cross-coupling reactions catalyzed by Pd/C. Shorter reaction times are obtained (13 min of irradiation) using microwave irradiation compared to conventional methods of heating (> 1 h). Yields with relatively non-volatile aryl bromides range from 65 to 83%. Lower yields (15 - 27%) are obtained with relatively volatile aryl bromides substrates which may be evaporating during the course of the reaction. Ease of reaction set-up, rate enhancement from the microwave irradiation and facile work-up provided by the use of Pd/C makes this a very efficient procedure to mn. 

Amann, N. and Wagenknecht, H. A. (2002). Preparation of pyrenyl-modified nucleosides via Suzuki-Miyaura cross-coupling reactions. Syn-lett 687-691. 

Kotha S, Lahiri S, Kashinath D (2002) Recent applications of the Suzuki-Miyaura cross-coupling reaction in organic synthesis. Tetrahedron 58 9633-9695... 

No examples of such reactions have been disclosed. Displacement of halogens on the parent heterocycle through metal-catalyzed processes have surprisingly not been reported to our knowledge on the neutral heterocycle. Recently, Suzuki-Miyaura cross-coupling reactions of imidazolium bromide 113 with various boronic acids or esters were reported <2005T6207> to proceed in good yield, without deprotonation at the C-3 position (Scheme 35). 

Chamoin, S. Houldsworth, S. Kruse, C. G. Bakker, W. I. Snieckus, V. The Suzuki-Miyaura Cross Coupling Reactions on Solid Support. Link to Solution Phase Directed ortho Metalation. The Leznoff Acetal Linker Approach to Biaryl and Heterobiaryl Aldehydes, Tetrahedron Lett. 1998, 39, 4179-4182. 

Synthesis and Cytostatic Activity of Substituted 6-Phenylpurine Bases and Nucleosides Application of the Suzuki—Miyaura Cross-Coupling Reactions of 6-Chloropurine Derivatives with Phenylboronic Acids... 

Havelkova, M. Hocek, M. Cesnek, M. Dvorak, D. The Suzuki-Miyaura Cross-Coupling Reactions of 6-Halopurines with Bo-ronic Acids Leading to 6-Aryl- and 6-Alkenylpurines. Synlett 1999, 1145-1147. 

The time consuming chromatographical purification of heterocycles 28 and 29 slowed down the rate of library production. A phase separation using fluorous chemistry was employed by Zhang and Lu to address the workup and purification of fused 3-aminoimidazo[ l,2-a]pyridines (such as 30) [54]. Thus, attachment of a perfluorooctanesulfonyl tag to aldehydes and subsequent Ugi three-component microwave-assisted condensations with 2-aminopyridines and isocyanides furnished the desired heterocycles 30, which were conveniently isolated by fluorous solid-phase extraction. The fluorous tag could be subsequently used as an activating group in the post-condensation modifications, such as Suzuki-Miyaura cross-coupling reactions. 

S. Kotha, K. Lahiri, D. Kashinath, Recent Applications of the Suzuki-Miyaura Cross-Coupling Reaction in Organic Synthesis, Tetrahedron 2002, 58, 9633-9695. 

The Suzuki-Miyaura Cross-Coupling Reactions of 2-, 6- or 8-Halopurines with Boronic Acids Leading to 2-, 6- or 8-Aryl- and -Alkenylpurine Derivatives... 

Nickel/carbene complexes have also been successfully employed in the Suzuki-Miyaura cross-coupling reaction. One of the first successful applications of this was demonstrated by Blakey and MacMillan, wherein boronic acids were coupled with aryltrimethylammonium salts [52]. It was found that the transformation could be accomplished using 10 mol % Ni(COD)2,... 

Figure 3.63). The palladium(II) complex was used in the Suzuki-Miyaura cross-coupling reaction between phenylboronic acid and benzyl bromide, 2-bromo and 4-bromo benzalde-hyde, respectively [180-182],...

Chemler, S. R., Trauner, D., Danishefsky, S. J. The B-alkyl Suzuki-Miyaura cross-coupling reaction development, mechanistic study, and applications in natural product synthesis. Angewandte Chemie, International Edition 2001,40,4544-4568. 

Molander, G. A., Bernard , C. R. Suzuki-Miyaura Cross-Coupling Reactions of Potassium Alkenyltrifluoroborates. J. Org. Chem. 2002, 67, 8424-8429. 

Grasa, G. A., Viciu, M. S., Huang, J., Zhang, C., Trudell, M. L., Nolan, S. P. Suzuki-Miyaura Cross-Coupling Reactions Mediated by Palladium/lmidazolium Salt Systems. Organometallics 2002, 21,2866-2873. 

Additionally, Suzuki-Miyaura cross coupling reactions can be performed on similar supported iodides. Aryl bromides could be employed in this reaction as well. After optimization of conditions, it turned out that a hydroxyl-derived IL was the best solvent for this reaction. Namely, reaction completion was obtained after 12 h at room temperature in [N11130H][NTf2] in the presence of 1% Pd(OAc)2 and using potassium carbonate as abase. Under these conditions, less than 1% of homocoupling product is observed and easily eliminated by washing with diethyl ether prior to transesterification with methanol. Overall, biphenyls were isolated under analytically pure form in 90-95% yields [126],... 

A convenient and effective palladium-catalysed Suzuki-Miyaura cross coupling reaction of deactivated aryl chlorides with phenylboronic acid utilised the 1,3-diazepinium salts 107 as in situ precursors of the palladium ligands. These salts were prepared from the diamines 106 and cyclocondensation with triethyl orthoformate <05SL2394>. 

Martin R, Buchwald SL (2008) Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions employing dialkylbiaryl phosphine ligands. Acc Chem Res 41 1461-1473... 

Suzuki-Miyaura cross-coupling reactions of alkylboronic acid derivatives or alkyltrifluoroborates widi aryl, alkenyl or alkyl halides and triflates ,... 

The /1-alkyl Suzuki-Miyaura cross-coupling reaction in natural product synthesis 01AG(E)4544. 

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