The Suzuki-Miyaura Coupling

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. 

Reaction of (diisopropylamino)chloroboryl ethers of alkynols (57) with alkynyl-stannanes (58) in the presence of nickel catalysts has been reported to afford formal f/ms-alkynylboration products (60), which could undergo the Suzuki-Miyaura coupling with organic halides. The 2-borylalkenylnickel(II) complex (59) was isolated as an intermediate in a reaction of the chloroboryl ether (57) with 1 equiv. of a nickel(0)-phosphine complex and characterized by X-ray crystallography.61... 

Table 21 Summary of the results obtained for the Suzuki-Miyaura coupling reactions conducted using an in situ fabricated PA-TAP-Pd membrane...

Liu and coworkers found almost at the same time that 5 mol% Ni(PPh3)4 catalyzed the Suzuki-Miyaura coupling of 11a with a-bromo esters, amides, or ketones 6a-c resulting in arylacetic acid derivatives 7a,c in 55-95% yield (entry 15) [57]. a-Chloroketones 6b reacted in 60-75% yield to benzylic ketones 7b. 

When IBioxl2 HOTf was employed as the ligand precursor for the Suzuki-Miyaura coupling of sterically hindered aryl chlorides and aryl boronic acids, excellent to good yields were obtained in refluxing toluene for a variety of starting materials (Table 6). Notably, this work represents the first report of tetra-orf/zo-substitulcd biaryl compounds achieved from aryl chlorides [143]. 

The amino functionalised imidazolium salt was then used to prepare a palladium NHC complex that was used in the Suzuki-Miyaura coupling between phenylboronic acid and phenyl bromide, albeit with rather moderate success. 

An efficient, diverse synthesis of oxazolo[4,5-c]quinoline-4-ones and thiazolo[4,5-c]quinolines-4-ones is carried out in two steps from readily available starting materials <03OL2911>. The Suzuki-Miyaura coupling reaction was employed. 

A highly regioselective microwave promoted synthesis of 2-aryl-6-chloro-benzothiazoles (xxxviii) by the Suzuki-Miyaura coupling reaction of 2,6-dic-hlorobenzothiazole with arylboronic acids is given by Heo et al. [58]. 

Matos, K., Soderquist, J. A. Alkylboranes in the Suzuki-Miyaura Coupling Stereochemical and Mechanistic Studies. J. Org. Chem. 1998,... 

Scheme 12 Reactivity of 43 in the Suzuki-Miyaura coupling of tetra-ortho-substituted biaryls...

Another example of a similar palladium migration process was reported by Buchwald as a side reaction in the Suzuki-Miyaura coupling of 2,4,6-tri-tert-butylbromobenzene (Scheme 8) [64], Contrary to expectations, Suzuki-Miyaura... 

Scheme 8.31 Scavenging of residual palladium from the Suzuki-Miyaura coupling.

Cyclopropyl arenes, alkynes and ALKENES from the IN srru GENERATION OF B CYCLOPROPYL 9 BBN AND THE SUZUKI-MIYAURA COUPLING OF ARYL, ALKYNYL AND ALKENYL BROMIDES... 

For instance, the Suzuki-Miyaura coupling of bromofuranone 25 with phenylboronic acid 26 in acetonitrile with sodium carbonate resulted in complete decomposition at 90°C, whereas in toluene with potassium carbonate, a 40% yield of the coupled product 27 was obtained at 140°C (Scheme 25.5A)P These conditions appear to be general and enabled halogenated examples to be synthesized in 46 to 63% yields. 

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