Please do not adjust margins
Organic & Biomolecular Chemistry
Page 10 of 11
ARTICLE
Journal Name
and S. R. Rout, Tetrahedron Lett., 2011, 52, 1924.
For recent reviews, see: (a) M.-L. LouilDlaOtIa: 1n0d.1F0.39W/C.9POaBtu00re71a2uA,
Chem. Soc. Rev., 2014, 43, 901. (b) J. Jiao, K. Murakami and K.
Itami, ACS Catal., 2016, 6, 610. (c) Y. Park, Y. Kim and S. Chang,
Chem. Rev., 2017, 117, 9247. (d) M. C. Henry, M. A. B. Mostafa
and A. Sutherland, Synthesis, 2017, 49, 4586.
For example, see: (a) C. Tang and N. Jiao, J. Am. Chem. Soc.,
2012, 134, 18924. (b) M.-L. Louillat, A. Biafora, F. Legros and
F. W. Patureau, Angew. Chem. Int. Ed., 2014, 53, 3505.
Á. M. Martinez, N. Rodriguez, R. G. Arrayás and J. C. Carretero,
Chem. Commun., 2014, 50, 2801.
N-Methyl-6-(1H-pyrazole)-7-methoxy-3,4-dihydro-1H-quinolin-
2-one (16f) was synthesised as described for N-methyl-6-
benzenesulfonamide-7-methoxy-3,4-dihydro-1H-quinolin-2-
one (16a) using N-methyl-7-methoxy-3,4-dihydro-1H-quinolin-
2-one (14) (0.0500 g, 0.262 mmol) and pyrazole (0.531 g, 0.780
mmol). The iodination step was carried out at 40 °C for 4 h and
the N-arylation step at 150 °C for 20 h. Purification by flash
column chromatography (ethyl acetate/hexane, 7:3) gave N-
methyl-6-(1H-pyrazole)-7-methoxy-3,4-dihydro-1H-quinolin-2-
one (16f) (0.0400 g, 60%) as a white solid. Mp 168–170 °C;
νmax/cm−1 (neat) 2947 (CH), 1667 (C=O), 1620, 1528, 1466, 1350,
1188, 1134, 1034; δH (400 MHz, CDCl3) 2.66 (2H, dd, J = 9.2, 6.8
Hz, 4-H2), 2.89 (2H, dd, J = 9.2, 6.8 Hz, 3-H2), 3.40 (3H, s, NCH3),
3.89 (3H, s, OCH3), 6.42 (1H, dd, J = 2.3, 1.7 Hz, 4’-H), 6.65 (1H,
s, 8-H), 7.54 (1H, s, 5-H), 7.69 (1H, d, J = 1.7 Hz, 3’-H), 7.99 (1H,
d, J = 2.3 Hz, 5’-H); δC (101 MHz, CDCl3) 24.4 (CH2), 29.7 (CH3),
31.8 (CH2), 56.4 (CH3), 100.1 (CH), 106.2 (CH), 118.8 (C), 124.3
(CH), 124.5 (C), 131.4 (CH), 140.0 (CH), 140.2 (C), 150.5 (C),
170.4 (C); m/z (ESI) 280.1052 (MNa+. C14H15N3NaO2 requires
280.1056)
5
6
7
8
9
Q. Li, S.-Y. Zhang, G. He, Z. Ai, W. A. Nack and G. Chen, Org.
Lett., 2014, 16, 1764.
K. Sun, Y. Li, T. Xiong, J. Zhang and Q. Zhang, J. Am. Chem. Soc.,
2011, 133, 1694.
10 M. A. B. Mostafa, E. D. D. Calder, D. T. Racys and A. Sutherland,
Chem. Eur. J., 2017, 23, 1044.
11 I. Goldberg, Ber. Dtsch. Chem. Ges., 1906, 39, 1691.
12 (a) D. T. Racys, C. E. Warrilow, S. L. Pimlott and A. Sutherland
Org. Lett., 2015, 17, 4782. (b) M. A. B. Mostafa, R. M. Bowley,
D. T. Racys, M. C. Henry and A. Sutherland, J. Org. Chem.,
2017, 82, 7529. (c) M. C. Henry, H. M. Senn and A. Sutherland,
J. Org. Chem., 2019, 84, 346.
13 Analysis of the one-pot amination of 1a by 1H NMR
spectroscopy showed that full conversion to the bromide
intermediate was achieved during the first step. Hence,
recovery of 1a at the end of the copper-catalysed amination
step is due to reduction of the bromide intermediate and not
returned unreacted aniline.
Conflicts of interest
There are no conflicts to declare.
14 In previous studies (see reference 10), control experiments
showed that the presence of the ionic liquid has no effect on
the copper-catalysed C-N bond forming step.
Acknowledgements
15 G. Evano, N. Blanchard and M. Toumi, Chem. Rev., 2008, 108,
3054.
16 (a) A. Shafir and S. L. Buchwald, J. Am. Chem. Soc., 2006, 128,
8742. (b) A. Shafir, P. A. Lichtor and S. L. Buchwald, J. Am.
Chem. Soc., 2007, 129, 3490.
17 Buchwald and co-workers have suggested that the success of
cyclic diamine ligands for Goldberg-type coupling reactions
may be due to an increase of the stability constant of the
catalytically active copper-nucleophile complex: (a) A.
Klapars, J. C. Antilla, X. Huang and S. L. Buchwald, J. Am. Chem.
Soc., 2001, 123, 7727. (b) A. Klapars, X. Huang and S. L.
Buchwald, J. Am. Chem. Soc., 2002, 124, 7421.
18 D. T. Racys, S. A. I. Sharif, S. L. Pimlott and A. Sutherland, J.
Org. Chem., 2016, 81, 772.
19 (a) M. Earle, B. J. McAuley, A. Ramani, K. Seddon and J.
Thompson, WO 02072260, 2002. (b) M. J. Earle, U. Hakala, B.
J. McAuley, M. Nieuwenhuyzen, A. Ramani, K. R. Seddon,
Chem. Commun., 2004, 1368.
Financial support from the EPSRC (studentship to M.C.H.,
EP/M508056/1), the University of Glasgow (studentship to
R.J.F) and the Ministry of Higher Education and Scientific
Research, Omar Al-Mukhtar University, Libya (studentship to
M.A.B.M.) is gratefully acknowledged.
Notes and references
1
(a) R. Hili and A. K. Yudin, Nat. Chem. Biol., 2006, 2, 284. (b) A.
Ricci, Ed. Amino Group Chemistry: From Synthesis to the Life
Sciences, Wiley-VCH, Weinheim, 2007.
For reviews of copper-catalysed aryl amination, see: (a) K.
Kunz, U. Scholz and D. Ganzer, Synlett, 2003, 2428. (b) S. V.
Ley and A. W. Thomas, Angew. Chem. Int. Ed., 2003, 42, 5400.
(c) C. Sambiagio, S. P. Marsden, A. J. Blacker and P. C.
McGowan, Chem. Soc. Rev., 2014, 43, 3525. (d) K. Okano, H.
Tokuyama and T. Fukuyama, Chem. Commun., 2014, 50,
13650.
2
20 S. Antoniotti, V. Dalla and E. Duñach, Angew. Chem. Int. Ed.,
2010, 49, 7860.
21 For example, see: (a) J. W. Tye, Z. Weng, A. M. Johns, C. D.
Incarvito and J. F. Hartwig, J. Am. Chem. Soc., 2008, 130, 9971.
(b) E. R. Strieter, B. Bhayana and S. L. Buchwald, J. Am. Chem.
Soc., 2009, 131, 78. (c) R. Giri, A. Brusoe, K. Troshin, J. Y. Wang,
M. Font and J. F. Hartwig, J. Am. Chem. Soc., 2018, 140, 793.
22 E. Sperotto, G. P. M. van Klink, G. van Koten and J. G. de Vries,
Dalton Trans., 2010, 39, 10338.
3
4
For reviews of palladium-catalysed aryl amination, see: (a) M.
Carril, R. SanMartin and E. Domínguez, Chem. Soc. Rev., 2008,
37, 639. (b) J. F. Hartwig, Acc. Chem. Res., 2008, 41, 1534. (c)
D. S. Surry and S. Buchwald, Angew. Chem. Int. Ed., 2008, 47,
6338. (d) C. Fischer and B. Koenig, Belstein J. Org. Chem., 2011,
7, 59.
For example, see: (a) M. Taillefer, N. Xia and A. Ouali, Angew.
Chem. Int. Ed., 2007, 46, 934. (b) A. Correa and C. Bolm,
Angew. Chem. Int. Ed., 2007, 46, 8862. (c) Z. Wang, H. Fu, Y.
Jiang and Y. Zhao, Synlett, 2008, 2540. (d) A. Correa, S. Elmore
and C. Bolm, Chem. Eur. J., 2008, 14, 3527. (e) S. L. Buchwald
and C. Bolm, Angew. Chem. Int. Ed., 2009, 48, 5586. (f) D. Guo,
H. Huang, Y. Zhou, J. Xu, H. Jiang, K. Chen and H. Liu, Green
23 W. S. Palmer, G. Poncet-Montange, G. Liu, A. Petrocchi, N.
Reyna, G. Subramanian, J. Theroff, A. Yau, M. Kost-Alimova, J.
P. Bardenhagen, E. Leo, H. E. Shepard, T. N. Tieu, X. Shi, Y.
Zhan, S. Zhao, M. C. Barton, G. Draetta, C. Toniatti, P. Jones,
M. G. Do and J. N. Andersen, J. Med. Chem., 2016, 59, 1440.
24 R. J. Faggyas, M. Grace, L. Williams and A. Sutherland, J. Org.
Chem., 2018, 83, 12595.
25 Z. Kuang, B. Li and Q. Song, Chem. Comm., 2018, 54, 34.
10 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins