586
F. Seyfert, H.-A. Wagenknecht
Letter
Synlett
Supporting Information
equiv) were dissolved in anhydrous toluene (0.26 M). The reac-
tion mixture was stirred under reflux and inert atmosphere
overnight and cooled to r.t. The solvent was removed under
vacuum. Compound 1 was purified by column chromatography
(hexane/CH2Cl2 = 5:1, silica gel, Rf = 0.34) and obtained as yellow
solid (123 mg, 0.330 mmol, 33%). 1H NMR (500 MHz, CDCl3): =
7.52 (d, J = 7.7 Hz, 1 H), 7.43 (s, 1 H), 7.33 (d, J = 8.2 Hz, 1 H), 7.26 (d,
J = 8.4 Hz, 2 H), 7.21–7.15 (m, 2 H), 7.03 (d, J = 7.5 Hz, 1 H), 6.94 (d,
J = 8.7 Hz, 2 H), 6.85 (t, J = 7.15 Hz, 1 H), 6.77 (t, J = 7.2 Hz, 1 H), 6.47
(s, 1 H), 6.27 (d, J = 8.0 Hz, 1 H), 3.09 (s, 6 H) ppm. 13C NMR (126
MHz, CDCl3): = 150.19, 143.96, 142.56, 133.36, 131.52, 130.10,
129.37, 126.93, 126.89, 126.42, 126.21, 125.92, 124.27, 124.03,
122.22, 121.65, 119.0, 116.0, 114.04, 110.88, 40.71 ppm. ESI-
HRMS: m/z calcd: 368.1347 [M+]; found: 368.1332 [M+].
Supporting information for this article is available online at
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References and Notes
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(17) Experimental Procedure
Compound 11 (250 mg, 1.00 mmol, 1.00 equiv), 4-bromo-N,N-
diisopropylaniline (1.42 mL, 384 mg, 1.50 mmol, 1.50 equiv),
NaOt-Bu (240 mg, 2.50 mmol, 2.50 equiv), tricyclohexylphos-
phine (20.0 mg, 0.07 mmol, 0.07 equiv), and Pd2dba3 (46 mg,
0.05 mmol, 0.05 equiv) were dissolved in anhydrous toluene
(0.26 M). The reaction mixture was stirred under reflux and
inert atmosphere overnight and cooled to r.t. The solvent was
removed under vacuum. Compound 2 was purified by column
chromatography (hexane/CH2Cl2 = 1:2, silica gel, Rf = 0.4) and
obtained as yellow solid (275 mg, 0.648 mmol, 65%). 1H NMR
(500 MHz, CDCl3): = 7.52 (d, J = 7.8 Hz, 1 H), 7.43 (s, 1 H), 7.35
(d, J = 7.9 Hz, 1 H), 7.23–7.15 (m, 4 H), 7.06 (d, J = 8.9 Hz, 1 H),
7.03 (d, J = 6.0 Hz, 3 H), 6.87 (t, J = 7.4 Hz, 1 H), 6.78 (t, J = 7.4 Hz, 1
H), 6.52 (s, 1 H), 6.32 (d, J = 7.2 Hz, 1 H), 3.93 (hept, 2 H), 1.36 (d,
J = 6.8 Hz, 12 H) ppm. 13C NMR (126 MHz, CDCl3): = 148.19,
143.98, 142.54, 133.38, 130.91, 130.11, 129.72, 126.96, 126.89,
126.42, 126.22, 125.88, 124.25, 124.01, 122.29, 121.64, 119.02,
118.79, 116.30, 110.93, 47.70, 21.47 ppm. ESI-HRMS: m/z calcd:
424.1973 [M+]; found: 424.1948 [M+].
(18) Experimental Procedure
Compound 11 (250 mg, 1.00 mmol, 1.00 equiv), 4-bromo-N,N-
diisobutylaniline (299 mg, 1.05 mmol, 1.05 equiv), NaOt-Bu
(240 mg, 2.50 mmol, 2.50 equiv), tricyclohexylphosphine (20
mg, 0.07 mmol, 0.07 equiv), and Pd2dba3 (46.0 mg, 0.05 mmol,
0.05 equiv) were dissolved in anhydrous toluene (0.26 M). The
reaction mixture was stirred under reflux and inert atmosphere
overnight and cooled to r.t. The solvent was removed under
vacuum. Compound 3 was purified by column chromatography
(hexane, silica, Rf = 0.3) and obtained as white solid (256 mg,
0.566 mmol, 56%). 1H NMR (500 MHz, CDCl3): = 7.51 (d, J = 7.0
Hz, 1 H), 7.43 (s, 1 H), 7.35 (d, J = 7.10 Hz, 1 H), 7.22–7.14 (m, 4 H),
7.02 (d, J = 7.25 Hz, 1 H), 6.90–6.75 (m, 4 H), 6.51 (s, 1 H), 6.32 (d,
J = 8.10 Hz, 1 H), 3.25 (d, J = 7.21 Hz, 4 H), 2.20 (hept, J = 6.70 Hz, 2
H), 0.99 (d, J = 6.55 Hz, 12 H) ppm. 13C NMR (126 MHz, CDCl3): =
148.09, 144.11, 142.68, 133.39, 131.31, 130.09, 128.06, 126.96,
126.89, 126.39, 126.21, 125.84, 124.24, 123.97, 122.30, 121.59,
118.97, 116.31, 113.89, 110.91, 60.65, 26.57, 20.67 ppm. ESI-
HRMS: m/z calcd: 452.2286 [M+]; found: 452.2269 [M+].
(19) Pavlishchuk, V. V.; Addison, A. W. Inorg. Chim. Acta 2000, 298, 97.
(20) Kim, H.; Kim, H.; Lambert, T. H.; Lin, S. J. Am. Chem. Soc. 2020,
142, 2087.
(14) Dadashi-Silab, S.; Pan, X.; Matyjaszewski, K. Chem. Eur. J. 2017,
23, 5972.
(15) Experimental Procedure
Compounds 9 (8.00 g, 50.0 mmol) and 10 (6.25 g, 50.0 mmol)
were dissolved in 1,2,4-trichlorobenzene (25 mL), heated to 200
°C, and stirred overnight. After cooling, the product mixture
was diluted with n-hexane, and the crystalline 11 was collected
by filtration, washed with fresh n-hexane and EtOH, and
obtained as yellow powder (5.02 g, 20.2 mmol, 40%). 1H NMR
(500 MHz, DMSO): = 8.99 (br s, 1 H), 7.57 (t, J = 8.6 Hz, 2 H),
7.49 (s, 1 H), 7.31–7.27 (m, 1 H), 7.20–7.16 (m, 1 H), 7.04–6.96
(m, 3 H), 6.78–6.73 (m, 2 H) ppm. 13C NMR (126 MHz, CDCl3):
= 140.60, 139.13, 133.31, 129.69, 127.54, 126.56, 126.22,
126.09, 125.89, 124, 123.53, 121.31, 119.91, 115.69, 114.67,
107.97 ppm. ESI-HRMS: m/z calcd: 249.0612 [M+]; found:
249.0603 [M+].
(21) McKenzie, I. A.; Wang, L.; Onuska, N. P. R.; Williams, O. F.;
Begam, K.; Moran, A. M.; Dunietz, B. D.; Nicewicz, D. A. Nature
2020, 580, 76.
(22) Nishiyama, Y.; Wada, T.; Asaoka, S.; Mori, T.; McCarthy, T. A.; Kraut,
N. D.; Bright, F. V.; Inoue, Y. J. Am. Chem. Soc. 2008, 130, 7526.
(23) Penner, A.; Bätzner, E.; Wagenknecht, H.-A. Synlett 2012, 23,
2803.
(16) Experimental Procedure
Compound 11 (250 mg, 1.00 mmol, 1.00 equiv), 4-bromo-N,N-
dimethylaniline (300 mg, 1.50 mmol, 1.50 equiv), NaOt-Bu (240
mg, 2.50 mmol, 2.50 equiv), tricyclohexylphosphine (20.0 mg,
0.07 mmol, 0.07 equiv), and Pd2dba3 (46 mg, 0.05 mmol, 0.05
Synlett 2021, 32, 582–586