Dec 292017


Green Chem., 2018, Advance Article
DOI: 10.1039/C7GC02627G, Paper
Kathiravan Murugesan, Thirusangumurugan Senthamarai, Manzar Sohail, Muhammad Sharif, Narayana V. Kalevaru, Rajenahally V. Jagadeesh
Nanoscale Fe2O3-catalyzed environmentally benign synthesis of nitriles and amides has been performed from easily accessible aldehydes and ammonia using O2.

Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides

Author affiliations


The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized molecules is of fundamental interest because nitrogen-containing motifs are found in a large number of life science molecules, natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein we report the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O2 or air. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesise functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Additionally, applying this iron-based protocol, primary amides have also been prepared in a water medium.

1H NMR (300 MHz, Chloroform-d) δ 7.17 – 6.96 (m, 2H), 6.93 – 6.70 (m, 1H), 4.33 – 4.11 (m, 4H). 13C NMR (75 MHz, Chloroform-d) δ 147.75 , 143.80 , 125.87 , 121.21 , 118.91 , 118.25 , 104.38 , 64.59 , 64.12 . Off white solid

STR1 STR2 str3


cas 19102-07-9

  • 1,4-Benzodioxan-6-carbonitrile (8CI)
  • 2,3-Dihydro-1,4-benzodioxin-6-carbonitrile
  • 1-(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)nitrile



Melting Point, °C
105 – 106

Tetrahedron, 2015, vol. 71,  29, p. 4883 – 4887










Journal of the American Chemical Society, 2001, vol. 123, 49, p. 12202 – 12206



RSC Advances, 2013, vol. 3, 44, p. 22389 – 22396

STR1 STR2 str3


Organic Letters, 2017, vol. 19,  12, p. 3095 – 3098

2,3-Dihydrobenzo[b][1,4]dioxine-6-carbonitrile (Scheme 1, 2n) According to the general procedure A, the reaction of 1n (0.20 mmol), zinc cyanide (2.0 equiv), PCyPh2 (0.20 equiv) and Pd(OAc)2 (0.05 equiv) in dioxane (0.25 M) for 16 h at 150 °C, afforded after work-up and chromatography the title compound in 75% yield (24.2 mg). White solid. 1H NMR (500 MHz, CDCl3) δ 7.17-7.11 (m, 2H), 6.91 (d, J = 8.1 Hz, 1H), 4.32-4.31 (m, 2H), 4.30- 4.26 (m, 2H). 13C NMR (125 MHz, CDCl3) δ 147.84, 143.91, 126.04, 121.37, 119.01, 118.37, 104.62, 64.71, 64.24.




Nickel-Catalyzed Decarbonylative Suzuki–Miyaura Coupling of Amides To Generate Biaryls

 PROCESS, spectroscopy, SYNTHESIS  Comments Off on Nickel-Catalyzed Decarbonylative Suzuki–Miyaura Coupling of Amides To Generate Biaryls
Jul 112016

Thumbnail image of graphical abstract

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

Thumbnail image of graphical abstract

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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