10.1002/adsc.202000663
Advanced Synthesis & Catalysis
SG-B (8.8 mg, 11 µmol) was charged with oxygen gas (1
atm) at room temperature and sealed with a Teflon liner
screw cap. The resulting mixture was stirred at 110 °C and
then the color of solution turned black. After stirring for 6
hours, the reaction mixture was cooled to room temperature
and purified by silica gel column chromatography
(pentanes/CH2Cl2 = 1:1) to afford nitrile 2a (61.6 mg,
0.463 mmol, 84%) as a white solid and aldehyde 3a (7.4
mg, 54 µmol, 10%) as a color less oil. Nitrile 2a; Mp = 59–
60 °C (hexanes); Rf = 0.23 (hexanes/CH2Cl2 = 1:1); IR
1057–1303; d) G. Yan, Y. Zhang, J. Wang, Adv. Synth.
Catal. 2017, 359,4068–4105.
[3] For selected examples of nitrile synthesis via oxidation
of primary amines, see: a) G. Green, W. P. Griffith, D.
M. Hollinshead, S. V. Ley, M. Schröder, J. Chem. Soc.
Perkin Trans. 1 1984, 681–686; b) S. Yamazaki, Y.
Yamazaki, Bull. Chem. Soc. Jpn. 1990, 63, 301–303; c)
K. C. Nicolaou, C. J. N. Mathison, Angew. Chem. Int.
Ed. 2005, 44, 5992–5997; d) K. R. Reddy, C. U.
Maheswari, M. Venkateshwar, S. Prashanthi, M. L.
Kantam, Tetrahedron Lett. 2009, 50, 2050–2053; e) J.
Zhang, Z. Wang, Y. Wang, C. Wan, X. Zheng, Z. Wang,
Green Chem. 2009, 11, 1973–1978; f) F. Drouet, P.
Fontaine, G. Masson, J. Zhu, Synthesis, 2009, 8, 1370–
1374; g) K.-N. T. Tseng, A. M. Rizzi, N. K. Szymczak,
J. Am. Chem. Soc. 2013, 135, 16352–16355; h) L. V. A.
Hale, T. Malakar, K.-N. T. Tseng, P. M. Zimmerman, A.
Paul, N. K. Szymczak, ACS Catal. 2016, 6, 4799–4813;
i) D. Ventura-Epspinosa, A. Marzá-Beltrán, J. A. Mata,
Chem. Eur. J. 2016, 22, 17758–17766; j) K. M.
Lambert, J. M. Bobbitt, S. A. Eldirany, L. E. Kissane, R.
K. Sheridan, Z. D. Stempel, F. H. Sternberg, W. F.
Bailey, Chem. Eur. J. 2016, 22, 5156–5159; k) I. Dutta,
S. Yadav, S. De, M. Hölscher, W. Leitner, J. K. Bera, J.
Am. Chem. Soc. 2018, 140, 8662–8666; l) Y. Huang, X.
Chong, C. Liu, Y. Liang, B. Zhang, Angew. Chem. Int.
Ed. 2018, 57, 13163–13166, m) T. Achard, j. Egly, M.
Sigrist, A. Maisse-Francois, S. Bellemin-Laponnaz,
Chem. Eur. J. 2019, 25, 13271–13274, n) M. Kannan, S.
Muthaiah, Organometallics 2019, 38, 3560–3567, o) W.
Chen, J. Egly, A. I. Poblador-Bahamonde, A. Maisse-
Francois, S. Bellemin-Laponnaz, T. Achard, Dalton
Trans. 2020, 49, 3243–3252.
1
(ATR, cm–1): 2224, 1605, 1508, 1258, 1172, 1023, 843; H
NMR (400 MHz, CDCl3): 7.58 (2H, d, J = 8.4 Hz), 6.95
(2H, d, J = 8.4 Hz), 3.86 (3H, s); 13C NMR (150 MHz,
CDCl3): 162.4, 133.4, 118.7, 114.3, 103.2, 55.1; HRMS
(ESI) calcd. for C8H8NO [M+H]+, 134.0600, found
134.0594.
General Procedure of Nitrile Synthesis with Aldehydes
A sealed tube equipped with a magnetic stirring bar
containing 4-methoxybenzaldehyde (3a) (66.0 mg, 0.485
mmol), which was obtained from commercial supplier and
used with purification by distillation under reduced
pressure, ammonium acetate (74.6 mg, 0.968 mmol),
xylene (0.49 mL) and SG-B (19.1 mg, 24.1 µmol) was
charged with oxygen gas (1 atm) at roo m temperature and
sealed with a screw cap. The resulting mixture was heated
at 130 °C and then the color of solution turned black. After
stirring for 2 hours, the reaction mixture was cooled to
room temperature and purified by silica gel column
chromatography (hexanes/CH2Cl2 = 1:1) to afford 2a (56.5
mg, 0.424 mmol, 88%) as a pale yellow solid; Mp = 56–
58 °C (CH2Cl2); Rf = 0.63 (CH2Cl2 only); IR (neat, cm–1):
2936, 2917, 2846, 2224, 1603, 1498, 1172, 1024, 835, 683;
1H NMR (400 MHz, CDCl3): 7.59 (2H, d, J = 8.8 Hz),
6.95 (2H, d, J = 8.8 Hz), 3.86 (3H, s); 13C NMR (100 MHz,
CDCl3): 162.8, 133.9, 119.2, 114.7, 103.9, 55.5; HRMS
(ESI) calcd. for C8H8NO [M+H]+, 134.0600, found
134.0606.
[4] For selected examples of nitrile synthesis via oxidation
of imines, see: a) C. B. Kelly, K. M. Lambert, M. A.
Mercadante, J. M. Ovian, W. F. Bailey, N. E.
Leadbeater, Angew. Chem. Int. Ed. 2015, 54, 4241–
4245; b) C. Fang, M. Li, X. Hu, W. Mo, B. Hu, N. Sun,
L. Jin, Z. Shen, RSC Adv. 2017, 7, 1484–1489; c) H.
Chen, S. Sun, H. Xi, K. Hu, N. Zhang, J. Qu, Y. Zhou,
Tetrahedron Lett. 2019, 60, 1434–1436; d) J. Nandi, N.
E. Leadbeater, Org. Biomol. Chem. 2019, 17, 9182–
9186.
Acknowledgements
This work was supported by JSPS KAKENHI
(JP18H04231 in Precisely Designed Catalysts with
Customized Scaffolding and JP18H04642 in Hybrid
Catalysis, a Grant-in aid for Scientific Research (B)
(18H02549) and (C) (17K08204)).
[5] For recent review of nitrile synthesis via aerobic
oxidation of primary amines, see: R. Ray, A. S. Hazari,
G. K. Lahiri, D. Maiti, Chem. Asian J. 2018, 13, 2138–
2148.
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