Cross-coupling reactions Suzuki-Miyaura reaction

Transition metal-catalysed reactions have emerged as powerful tools for carbon-carbon (C-C) bond formation [1], Cross-coupling reactions (Suzuki-Miyaura, Mizoroki-Heck, Stille, etc.) are recognised to be extremely reliable, robust and versatile. However, some other catalysed arylation reactions have been studied and have been reported to be very efficient [2]. In recent years, A -heterocyclic carbenes (NHC) have been extensively studied and their use as ligands for transition-metal catalysis has allowed for the significant improvement of many reactions [3]. This chapter highlights the use of NHC-bearing complexes in those arylation reactions. 

Scheme 3.6 Successive copper-catalyzed cross-coupling and Suzuki-Miyaura cross-coupling reaction.

The scope of Suzuki-Miyaura reactions is extremely broad, covering practically all types of organic residues. The cross-coupling of arylboronic acids with aryl halides or triflates is the most... 

Anionic complexes of boron (boronates, borinates, etc.) have been introduced as convenient reagents in cross-coupling reactions of broad scope, particularly interesting for the transfer of alkynyl and primary alkyl residues, which cannot be accomplished using the standard protocols of the Suzuki-Miyaura reaction. Readily available Ph4BNa can be used as a convenient reagent for phenylation in place of the much more expensive PhB(OH)2, and all four phenyl groups can be utilized when the reaction is carried out with a phosphine-free catalyst in aqueous solutions.244... 

Other successful examples of catalysts containing NHC ligands are found in palladium- and nickel-catalyzed carbon-carbon bond formations. The catalyst development with these metals has focused in particular on Heck-type reactions, especially the Mizoroki-Heck reaction itself [Eq. (42)] and various cross coupling reactions [Eq. (43)], e.g., the Suzuki-Miyaura reaction ([M] = and the Kumada-Corriu reaction ([M] = MgBr). " Related reactions like the Sonogashira coupling [Eq. (44)]326-329 Buchwald-... 

Miyaura, N. and Suzuki, A. Chem. Rev. 1995, 95, 2457-2483. Suzuki, A. in Metal-catalyzed cross-coupling reactions Diederich, F. Stang, P. J. Eds. Wiley-VCH Weinheim Germany, 1988, chapter 2, 49-97. 

Miyaura, N. Suzuki, A. Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds, Chem. Rev. 1995, 95, 2457-2483. 

Cross-coupling reactions 5-alkenylboron boron compounds, 9, 208 with alkenylpalladium(II) complexes, 8, 280 5-alkylboron boron, 9, 206 in alkyne C-H activations, 10, 157 5-alkynylboron compounds, 9, 212 5-allylboron compounds, 9, 212 allystannanes, 3, 840 for aryl and alkenyl ethers via copper catalysts, 10, 650 via palladium catalysts, 10, 654 5-arylboron boron compounds, 9, 208 with bis(alkoxide)titanium alkyne complexes, 4, 276 carbonyls and imines, 11, 66 in catalytic C-F activation, 1, 737, 1, 748 for C-C bond formation Cadiot-Chodkiewicz reaction, 11, 19 Hiyama reaction, 11, 23 Kumada-Tamao-Corriu reaction, 11, 20 via Migita-Kosugi-Stille reaction, 11, 12 Negishi coupling, 11, 27 overview, 11, 1-37 via Suzuki-Miyaura reaction, 11, 2 terminal alkyne reactions, 11, 15 for C-H activation, 10, 116-117 for C-N bonds via amination, 10, 706 diborons, 9, 167... 

Watanabe, T. Miyaura, N. Suzuki, A. Synthesis of sterically hindered biaryls via the Pd-cat-alyzed cross-coupling reaction of arylboronic acids or their esters with haloarenes. Synlett 1992, 207-210. 

Miyaura, N. Yamada, K. Suginome, H. Suzuki, A. Novel and convenient method for the stereo- and regiospecific synthesis of conjugated alkadienes and alkenynes via the Pd-catalyzed cross-coupling reaction of 1-alkenyl-boranes with bromoalkenes and bromoalk-ynesj. Am. Chem. Soc. 1985, 107, 972-980. 

It is noteworthy that the microwave-assisted Suzuki-Miyaura reactions were found to be far superior to the reactions under conventional heating, as can be demonstrated by yield improvements from 22% to 84% in the case of cross-coupling of PEA derivatives. Microwave-irradiation also provided smooth conversions in water as the sole solvent. 

Inhibition by radical traps, such as TEMPO 17, was used to explain the involvement of radicals in the course of transition metal-catalyzed reactions (Fig. 7). Typical cross-coupling reactions, such as Heck or Suzuki-Miyaura reactions, proceeded even with nitroxyls as substrates, although the yields were sometimes low. Thus, nitroxyls do not necessarily interfere very much with the course of two-electron catalytic processes [79-81]. However, it must be critically mentioned that 17 and related nitroxides are both oxidants and reductants for metal species. 

For the synthesis of a cavitand functionalized with terpyridyl groups via rigid linkages, transition metal catalyzed cross-coupling reactions are especially well suited. Starting with the boronic acid ester 48 [65], attachment of the terpyridyl groups to the cavitand was realized by Suzuki-Miyaura reaction with the tetraiodo-cavitand 47 (Fig. 15). 

Miyaura N, Suzuki A (1995) Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem Rev 95 2457-2483... 

Suzuki cross-coupling reactions have been reviewed by N. Miyaura and A. Suzuki, Chem. Rev., 1995, 2457 A. Suzuki, Pure Appl. Chem., 1994, 66, 213 and A. R. Martin and Y. Yang, Acta Chem. Scand.,... 

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