Coupling Suzuki—Miyaura

Palladium-catalyzed cross-coupling reaction of organoboranes with organic halides, triflates, etc. In the presence of a base (transmetallation is reluctant to occur without the activating effect of a base). For the catalytic cycle, see Kumada coupling on page 325. 

Name Reactions, 4th ed., DOI 10.1007/978-3-642-01053-8 250, Sprmger-Verlag Berlin Heidelberg 2009 

Suzuki, A. In Metal-catalyzed Cross-coupling Reactions-, Diederich, F. Stang, P. J., Eds. Wiley-VCH Weinhein, Germany, 1998, 49-97. (Review). 

Coupling of Aryl and Alkyl Halides with Organoboron Reagents (Suzuki Reaction). In Transition Metals for Organic Synthesis (2nd edn.) Beller, M. Bolm, C. eds., 2004,1,211-229. Wiley-VCH Weinheim, Germany. (Review). 

Nakhla, J. S. Suzuki coupling. In Name Reactions for Homologations-Part 1 Li, J. J., Corey, E. J., Eds. Wiley Sons Hoboken, NJ, 2009, pp 163-184. (Review). 

Name Reactions A Collection of Detailed Mechanisms and Synthetic Applications, DOI 10.1007/978-3-319-03979-4 269, Springer International Publishing Switzerland 2014 

Example 5, Nickel-catalyzed Suzuki-Miyaura coupling in green solvents  

The palladium-catalyzed Suzuki-Miyaura coupling of organoboranes with organic halides or derivatives is one of the preeminent methods for the synthesis of biaryls 

Cross-coupling of heterocycUc compounds is challenging. Anderson and Buch-wald [125] demonstrated that by combining 42 with Pd(OAc)2, a variety of hydrophilic aryl and heteroaryl halides could be coupled with boronic acids, giving the desired products in high yields. Examples are shown in Table 6.4. 

The complex Pd(II)-(di-2-pyridyl)methylamine 44 allows Suzuki coupling in aqueous media, using K2CO3 or KOH as a base in the presence of tetra-n-butylammonium bromide (TBAB) [127]. A range of aryl bromides and chlorides. 

Palladium simply encapsulated in a thiol-functionaUzed mesoporous silicate SBA-15-SH also catalyzes the Suzuki reactions, in either water or a DMF/H2O (20/1) mixture [130]. The reactions of a spectrum of (hetero)aryl bromides and activated aryl chlorides with phenylboronic acid proceeded smoothly at 1-2 mol% Pd and 80-100 °C, affording up to 98% yield without leaching of Pd ( 3ppb). A test on the heterogeneity of the reaction suggested that the catalysis occurred in a heterogenous process. 

A pH-responsive palladium catalyst 46, prepared by immobilizing palladium nanoparticles on colloidal core-shell micro-spheres that contain a pH-responsive shell of poly(methylacryUc acid) (PMAA) segments and a coordinative core of poly[2-(acetoxy)ethyl methacrylate] (PAEMA), exhibits good activity in the Suzuki and Heck reactions in a mixture of DMF/water (1 1, v/v) or in pure water [131]. The catalyst is highly dispersed under neutral or basic conditions, behaving like a homogeneous catalyst, but heterogeneous under acidic conditions. As such, it could 

The Inamoto group [25,44] has reported the first study of nickel pincer-catalyzed Suzuki-Miyaura reactions. In the presence of 1 mol% 30, aryl bromides and activated aryl chlorides can be coupled with PhB(OH)2 to generate the desired 

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The transition metal catalyzed cross coupling of an organohalide with a boronic acid derivative, the Suzuki-Miyaura coupling, has become one of the most popular ways of preparing biaryls.3 The reaction is very robust and can easily be scaled to provide multigrams of material.4... 

The Stille reaction has developed as a popular protocol for the formation of C-C bonds due to the air- and moisture-stability as well as functional group compatibility of organotin compounds. Together with the Suzuki-Miyaura coupling it is one of the most powerful methods for the synthesis of molecules containing unsymmetrical biaryl moieties. However, despite its efficiency, this versatile reaction has slowly been displaced by other procedures that avoid the use of highly toxic organostannanes. 

In this study we show that the Pd/C catalyzed Suzuki-Miyaura coupling reaction can be performed in a microwave oven. Overall the microwave synthesis is faster than comparable thermal methods and the combination of the ease of use of the microwave oven and the facile work-up with Pd/C makes this a very efficient method for performing coupling reactions. 

A variety of triazole-based monophosphines (ClickPhos) 141 have been prepared via efficient 1,3-dipolar cycloaddition of readily available azides and acetylenes and their palladium complexes provided excellent yields in the amination reactions and Suzuki-Miyaura coupling reactions of unactivated aryl chlorides <06JOC3928>. A novel P,N-type ligand family (ClickPhine) is easily accessible using the Cu(I)-catalyzed azide-alkyne cycloaddition reaction and was tested in palladium-catalyzed allylic alkylation reactions <06OL3227>. Novel chiral ligands, (S)-(+)-l-substituted aryl-4-(l-phenyl) ethylformamido-5-amino-1,2,3-triazoles 142,... 

Miura M (2004) Rational ligand design in constructing efficient catalyst systems for suzuki-miyaura coupling. Angew Chem Int Ed 43 2201-2203... 

The regiospecific functionalization of the terminal alkyl group of simple amines or ethers with bis(pinacolato)-diborane leads to organoboranes. The latter have manifold applications in organic synthesis since the catalytic borylation process can be combined with a functional group transformation step, including Suzuki-Miyaura couplings, for the synthesis of elaborated molecules. Curiously, functionalization of the C-H atoms a to the heteroatom was not observed (Equation (22)). a... 

Scheme 17 Synthesis of C-glycals based on Suzuki-Miyaura coupling/RCM sequence.

Table 4 Suzuki and Suzuki-Miyaura coupling reactions of halogenopyrazines...

Reaction with Organoboron Reagents (Suzuki-Miyaura Coupling) 660... 

A major advantage of this MCR is that organoboronic acids are readily available in a large variety of structural configurations and they can be formed in isomeri-cally pure forms. As a result of their widespread utility in Suzuki-Miyaura coupling [27, 28] and other reactions [29, 30], a variety of aryl and heteroaryl [31] boronic adds are now commercially available and can be employed in this MCR process. Most of these compounds are also air and water stable as well as non-toxic and environmentally friendly. They also tolerate many functional groups, thereby... 

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