Suzuki-Miyaura crosscoupling

Shylesh, S., Wang, L. and Thiel, W.R. (2010) Palladium(II)-phosphine complexes supported on magnetic nanoparticles filtration-free, recyclable catalysts for Suzuki-Miyaura crosscoupling reactions. Advanced Synthesis and Catalysis, 352 (2-3), 425-432. 

Kotha, S. Lahiri, K. Kashinath, D. Recent applications of the Suzuki-Miyaura crosscoupling reaction in organic synthesis. Tetrahedron 2002, 58, 9633-9695. 

Scheme 39. Biaryl O-carbamate anionic remote Fries rearrangement. Conquering steric encumbrance in direct Suzuki-Miyaura crosscoupling.

Table 6 Synthesis of tetra-orf/io-substituted biaryl compounds by Suzuki-Miyaura crosscoupling...

In 2010, Weinreb and coworkers reported their synthesis of communesin F (17) [30]. The synthesis began with known enol triflate 37. A Suzuki-Miyaura crosscoupling with 0-nitrophenyl boronic acid (38) followed by a two-step reaction with iodoaniline 39, afforded amide 40. A one-pot displacement of the benzyl group with ethyl carbamate, amide nitrogen protection, and a subsequent intramolecular Heck reaction provided enamide 41 (Scheme 5). 

For the synthesis of the non-diene analogue 65, which bears a benzyl group in the terminal position (Scheme 17), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) cleavage of the p-methoxybenzyl (PMB) ether at the C15-position did not proceed in the presence of the benzyl moiety (oxidation of the methylene in allylic-benzylic-position in C23-position). Therefore, we inverted the order of the first two steps (1) DDQ deprotection on 44 and (2) nickel-catalyzed cross-coupling reaction performed on a free primary alcohol in C15 position. After this minor modification, completion of the synthesis followed the established route Suzuki-Miyaura crosscoupling reaction between alkyl iodide 73 (via its trialkylboronate species) and vinyl iodide 60 to yield 74 selective carbamate installation and final deprotection to afford DDM analogue 65. 

Potassium 2-methoxyphenyltrifluoroborate [236388-46-8] M 214.0, m >300 can be prepared in the same manner from 2-methoxyphenylboronic acid and used successfully in Pd-catalysed Suzuki-Miyaura crosscoupling reactions. 

Scheme 2.15 Representative aryl pseudohaUdes employed in Suzuki-Miyaura crosscoupling reactions.

Scheme 2.33 Syntheses of atropisomeric biaryls through the Suzuki-Miyaura crosscoupling reaction.

Scheme 2.34 Stereochemical studies conducted on the 6-alkyl Suzuki-Miyaura crosscoupling reaction.

Recently, He and Falck [110] conducted stereospedfic Suzuki-Miyaura crosscoupling reactions with enantioenriched a-cyanohydrin triflates 191 (Eq. (41), Scheme 2.38). This substrate class was chosen because the cyano substituent not only is a versatile functional group but can also act as an electron-withdrawing group to facilitate the key oxidative addition step. By employing enantiomerically enriched a-cyanohydrin triflates 191 imder the optimized conditions, the authors found that various a-arylated nitriles could be produced with inversion of stereochemistry. The stereochemical outcome can be explained as outlined earlier. The oxidative addition takes place with inversion of stereochemistry, while transmetallation and reductive elimination occur with retention of stereochemistry, allowing the final product to form with an overall inversion of stereochemistry. 

Example 9 Suzuki-Miyaura Crosscoupling Polymerization of DPP and TTF Derivatives (15, 16) to give P22 ... 

Figure 16.4 Early examples of acyclic carbene complexes explored In Suzuki-Miyaura crosscoupling.

Baghbanzadeh M, Pilger C, Kappe CO (2011) Rapid nickel-catalyzed suzuki-miyaura crosscouplings of aryl carbamates and sulfamates utilizing microwave heating. J Oig Chem 76(5) 1507 1510. doi 10.102 l/jol024464... 

Scheme 1.11 The synthesis of dragmacidin F by Stotiz s group employing two Suzuki-Miyaura crosscoupling arylation reactions as key steps [28].

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