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1H), 7.80–7.77 (m, 2H), 7.52–7.49 (m, 1H), 7.27 (d, J ¼ 7.7 Hz, (6.95%). MS (ESI) (m/z) calcd for [M–AcO]+: 343.04, found:
1H), 6.58 (br s, 1H), 3.13 (s, 2H), 1.72 (s, 6H). 13C NMR (101 343.04.
MHz, CDCl3): d 167.4, 153.5, 149.1, 147.2, 143.3, 137.9, 137.9,
126.2, 125.2, 123.9, 118.4, 110.8, 68.8, 45.1, 25.9. HRMS (ESI) (m/
Synthesis of metalated compound 8
z) calcd for [M + H]+: 298.1186, found: 298.1189.
A mixture of 200 mg (0.50 mmol) of 7 and 130 mg of LiBr (1.50
Diethyl 1-picolinoylindoline-2,2-dicarboxylate (2j). Pale oil,
mmol) was stirred in acetone at room temperature for 1 hour
1
39 mg (0.15 mmol, 57%) from amine 5j (50 mg). H NMR (400
and then ltered to obtain 8 as yellow crystals (165 mg,
MHz, CDCl3, 50 ꢀC): d 8.49 (br m, 1H), 8.05 (br m, 1H), 7.87–7.82
0.40 mmol, 80% yield). 1H NMR (400 MHz, CDCl3): d 9.50 (d, J ¼
(m, 1H), 7.40–7.35 (m, 1H), 7.15 (d, J ¼ 7.7 Hz, 1H), 7.05 (br m,
5.5 Hz, 1H), 8.51 (s, 11H), 8.06 (dd, J ¼ 7.8, 1.2 Hz, 1H), 8.0 (td, J
1H), 7.04–6.98 (m, 1H), 4.22–4.08 (br m, 4H), 3.74 (s, 2H), 1.34–
¼ 7.8, 2.0 Hz, 1H), 7.74 (d, J ¼ 7.7, 1H), 7.66–7.62 (dd, J ¼ 7.8,
5.5 Hz, 1H), 6.97 (td, J ¼ 7.2, 1.3 Hz, 1H), 6.90–6.85 (m, 2H), 3.15
(br s, 2H), 1.45 (br s, 6H). EA (calc. for C16H17BrN2Pd): C: 45.4%
(45.36%); H: 4.1% (4.04%); N: 6.4% (6.61%). MS (ESI) (m/z) calcd
for [M–Br]+: 343.04, found: 343.04; calcd for [M–Br + CH3CN]+:
384.07, found: 384.07.
1.02 (br m, 6H). 13C NMR (101 MHz, CDCl3, 45 ꢀC): d 168.1,
165.5, 152.9, 147.2, 137.2, 127.8, 127.3, 125.4, 124.2, 124.1,
116.9, 75.2, 62.0, 40.7, 13.8. HRMS (ESI) (m/z) calcd for [M + H]+:
369.1445, found: 369.1450.
Ethyl 2-methyl-1-picolinoylindoline-2-carboxylate (2k). Pale
oil, 91 mg (0.29 mmol, 59%) from amine 5k (103 mg). 1H NMR
(400 MHz, CDCl3): d 8.62 (br m, 1H), 7.83 (td, J ¼ 7.7, 1.7 Hz,
1H), 7.63 (br m, 1H), 7.42 (dd, J ¼ 7.2, 5.3 Hz, 1H), 7.14 (d, J ¼
7.7 Hz, 1H), 6.95–6.75 (m, 2H), 5.63 (br m, 1H), 4.19 (br m, 2H),
3.53 (d, J ¼ 15.7 Hz, 1H), 3.02 (d, J ¼ 15.7 Hz, 1H), 1.79 (s, 3H),
1.21 (br s, 3H). 13C NMR (101 MHz, CDCl3): d 172.5, 166.0, 153.7,
149.5, 137.3, 129.4, 127.1, 125.4, 125.2, 123.8, 123.2, 114.7, 69.7,
61.5, 41.7, 21.6, 14.1. HRMS (ESI) (m/z) calcd for [M + H]+:
311.1390, found: 311.1385.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was supported by the Generalitat de Catalunya
(2017SGR474 and 2014SGR107) and the Spanish Ministerio de
Economia y Competitividad (PGC2018-098630-B-I00, CTQ2015-
65040-P, SAF2014-52223-C2-1-R and fellowship to A. M.).
(2,2-Diethylindolin-1-yl)(pyridin-2-yl)methanone (2l). Pale
1
oil, 38 mg (0.14, mmol, 27%) from amine 5l (88 mg). H NMR
(400 MHz, CDCl3): d 8.62 (d, 1H, J ¼ 4.6 Hz), 7.85–7.80 (m, 1H),
7.61 (d, J ¼ 7.8 Hz, 1H), 7.41–7.38 (m, 1H), 7.12 (d, J ¼ 7.3 Hz,
1H), 6.87–6.71 (m, 2H), 5.54 (br m, 1H), 3.10 (s, 2H), 2.54–2.40
(m, 2H), 1.88–1.78 (m, 2H), 0.93 (t, J ¼ 7.4 Hz, 6H). 13C NMR (101
MHz, CDCl3): d 167.1, 155.0, 149.4, 143.4, 137.2, 131.0, 126.4,
125.0, 124.9, 123.1, 122.9, 114.9, 73.6, 37.9, 30.4, 8.3. HRMS
(ESI) (m/z) calcd for [M + H]+: 281.1648, found: 281.1649.
Notes and references
1 (a) T. Gensch, M. N. Hopkinson, F. Glorius and J. Wencel-
Delord, Chem. Soc. Rev., 2016, 45, 2900–2936; (b)
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Synthesis of coordination compound 6
Palladium acetate (112 mg, 0.50 mmol) was added to a solution
of imine 1a (120 mg, 0.50 mmol) in toluene (20 mL), the
resulting solution was stirred 2 h at room temperature and then
ltered to obtain 6 as yellow crystals (135 mg, 0.32 mmol, 60%
1
yield). H NMR (400 MHz, CDCl3): d 8.42 (d, J ¼ 5.2, 1H), 8.05
(td, J ¼ 7.8, 1.5 Hz, 1H), 7.65 (d, J ¼ 7.5 Hz, 2H), 7.58–7.55 (m,
2H), 7.44 (s, 1H), 7.28 (t, J ¼ 7.5 Hz, 2H), 7.19 (t, J ¼ 7.5 Hz, 1H),
3.27 (s, 2H), 2.13 (s, 3H), 2.08 (s, 3H), 1.5 (s, 6H). MS (ESI) (m/z)
calcd for [M–2AcO]+: calcd for 344.04, found: 344.04; calcd for
[M–2AcO + CH3CN]+: 385.07, found: 385.07.
¨
2 (a) C. Sambiagio, D. Schonbauer, R. Blieck, T. Dao-Huy,
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J. Wencel-Delord, T. Besset, B. U. W. Maes and
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M. Schnurch, Chem. Soc. Rev., 2018, 47, 6603–6743; (b)
Synthesis of metalated compound 7
Y. Li and S. Xu, Chem.–Eur. J., 2018, 24, 16218–16245; (c)
L. Ping, D. S. Chung, J. Bouffard and S. Lee, Chem. Soc.
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3 For reviews, see: (a) T. Bhattacharya, S. Pimparkar and
D. Maiti, RSC Adv., 2018, 8, 19456–19464; (b) Q. Zhao,
T. Poisson, X. Pannecoucke and T. Besset, Synthesis, 2017,
49, 4808–4826; (c) M. R. Yadav, R. K. Rit, M. Shankar and
A. K. Sahoo, Asian J. Org. Chem., 2015, 4, 846–864; (d)
C. Wang and Y. Huang, Synlett, 2013, 24, 145–149For
recent examples, see: (e) Y. Liu and H. Ge, Nat. Chem.,
200 mg (0.43 mmol) of 6 were dissolved in toluene and heated at
90 ꢀC for 1 hour. The resulting solution was ltered, the solvent
was evaporated, and the residue was treated with diethyl ether
to obtain 7, as yellow crystals, 120 mg, (0.30 mmol, 70% yield).
1H NMR (400 MHz, CDCl3): d 8.60 (d, J ¼ 5.1 Hz, 1H), 8.34 (s,
1H), 7.94 (td, J ¼ 7.8, 1.6 Hz, 1H), 7.67 (d, J ¼ 7.7 Hz, 2H), 7.57
(ddd, J ¼ 7.8, 5.1, 1.3 Hz, 1H), 7.35 (m, 1H), 6.92 (m, 2H), 6.79 (m
1H), 2.95 (br s, 2H), 2.15 (br s, 3H), 1.40 (br s, 6H). EA (calc. for
C
18H20N2O2Pd): C: 53.4% (53.68%); H: 5.1% (5.01%); N: 6.6%
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