Jul 112016

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Shi et al. have reported a nickel-catalyzed decarbonylative Suzuki–Miyaura reaction which uses an N-aroylpiperidine-2,6-dione as the coupling partner for the boronic acid ( Angew. Chem., Int. Ed. 2016, 55, 6959−6963).
The method is attractive from the point of view of the stability of N-aroylpyrrolidine-2,5-diones toward storage and manipulation and the flexibility they add to the chemist’s toolbox, given their preparation from a different group of precursors to aryl halides or triflates.
Notably, the reaction uses an air-stable and inexpensive nickel catalyst, and the reactions tolerate the presence of water. While a standard reaction temperature of 150 °C is quoted, the use of temperatures as low as 80 °C also seem to be possible. Coupling efficiency is reported to be adversely affected when the aromatic rings of both of the coupling partners bear electron-donating substituents.
Ortho substituents on the aromatic rings seem to be beneficial as they facilitate decarbonylation as part of the cross-coupling. Oxidative addition into the N–C(aroyl) bond of the amide is proposed as initiating the catalytic cycle and is possible on account of a reduction in the resonance stabilization of the N-aroyl functionality versus a conventional aromatic amide.

Suzuki–Miyaura Coupling

Synthesis of Biaryls through Nickel-Catalyzed Suzuki–Miyaura Coupling of Amides by Carbon–Nitrogen Bond Cleavage (pages 6959–6963)Shicheng Shi, Guangrong Meng and Prof. Dr. Michal Szostak

Version of Record online: 21 APR 2016 | DOI: 10.1002/anie.201601914

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Breaking and making: The first nickel-catalyzed Suzuki–Miyaura coupling of amides for the synthesis of biaryl compounds through N−C amide bond cleavage is reported. The reaction tolerates a wide range of sensitive and electronically diverse substituents on both coupling partners.



1H NMR (500 MHz, CDCl3) δ 7.70 (s, 4 H), 7.61 (d, J = 7.3 Hz, 2 H), 7.48 (t, J = 7.6 Hz, 2 H), 7.42 (t, J = 7.3 Hz, 1 H).



13C NMR (125 MHz, CDCl3) δ 144.87, 139.92, 129.48 (q, J F = 32.5 Hz), 129.13, 128.32, 127.56, 127.42, 125.83 (q, J F = 3.8 Hz), 124.46 (q, J F = 270.0 Hz).



19F NMR (471 MHz, CDCl3) δ -62.39.

//////Nickel-Catalyzed,  Decarbonylative Suzuki–Miyaura Coupling,  Amides, Biaryls


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