FULL PAPER
400 MHz): δ 9.68 (s, 2H), 9.30 (s, 2H), 8.13 (s, 4H), 7.92 (d,
J=8.0 Hz, 2H), 7.25 (s, 2H), 6.95 (d, J=7.6 Hz, 2H), 2.39 (s,
6H) ppm; 13C NMR (DMSO-d6, 100 MHz): δ 166.7, 145.9,
144.0, 134.8, 133.0, 128.4, 122.7, 118.5, 117.1, 21.9 ppm; EI-
MS: m/z=395 (M+H)+.
aromatic, heteroaromatic, alkenyl- and alkylboronic
acids. This mild process has a high efficacy in large-
scale reactions. Compared to previous methods, this
protocol features wide range of substrates, largely
reduced reaction time, and high yields. Further inves-
tigations on the synthetic applications of this method-
ology are ongoing in our laboratory.
2,2’-(1,4-Phenylene)bis(6-chloro-2,3-dihydrobenzo[d][1,3,2]
diazaborinin-4(1H)-one) (5c): White solid; 369 mg, 85%
°
Yield; mp: >300 C; IR (KBr): 3408, 3329, 1652, 1619, 1540,
1
1505, 1359, 1295, 848, 825, 717 cmÀ 1; H NMR (DMSO-d6,
Experimental Section
400 MHz): δ 9.87 (s, 2H), 9.48 (s, 2H), 8.14 (s, 4H), 7.99 (s,
2H), 7.85 (d, J=8.0 Hz, 2H), 7.48 (d, J=8.8 Hz, 2H) ppm; 13
C
General
NMR (DMSO-d6, 100 MHz): δ 170.5, 149.5, 138.6, 137.5,
132.0, 130.0, 125.6, 125.3 ppm; EI-MS: m/z=436 (M+H)+.
Unless otherwise stated, all reagents were purchased from
commercial suppliers and used as received without further
purification. Melting points were determined on an X-5 digital
melting point apparatus and are not corrected. The FT-IR
spectra were recorded on a Bruker Tensor 27 Fourier transform
infrared spectroscope using a thin film supported on KBr
2,2’-(1,4-Phenylene)bis(6-methoxy-2,3-dihydrobenzo[d]
[1,3,2]diazaborinin-4(1H)-one) (5d): White solid; 374 mg,
°
88% Yield; mp: >300 C; IR (KBr): 3404, 3301, 2839, 1645,
1
1609, 1542, 1506, 1351, 1255, 862, 824, 753 cmÀ 1; H NMR
1
pellets. The H NMR and 13C NMR spectra were recorded on a
(DMSO-d6, 400 MHz): δ 9.78 (s, 2H), 9.31 (s, 2H), 8.12 (s,
4H), 7.50 (s, 2H), 7.41 (d, J=8.8 Hz, 2H), 7.24 (d, J=8.8 Hz,
2H), 3.81 (s, 6H) ppm; 13C NMR (DMSO-d6, 100 MHz): δ
171.4, 158.8, 144.9, 137.7, 127.5, 124.8, 124.4, 114.1,
60.6 ppm; EI-MS: m/z=427 (M+H)+.
Bruker AV III-500 or Zhongke Niujin AS 400 spectrometer
using TMS as internal standard. The mass spectra were
performed on a 3200 Qtrap instrument with an ESI source.
General Procedure for Synthesis of
1,3,2-Benzodiazaborininones
Procedure for Synthesis of Product 6
A mixture of 2-(3-bromophenyl)-2,3-dihydrobenzo[d][1,3,2]
diazaborinin-4(1H)-one (3i, 1 mmol), (4-(tert-butyl)phenyl)bor-
onic acid (1 mmol), K3PO4 (1.0 mmol) NiBr2(PPh3)2
(0.05 mmol), PdCl2 (0.05 mmol) in THF (2 ml) was stirred at
room temperature for 12 h. The reaction was quenched with
water and extracted with ethyl acetate for three times. The
combined organic layers were dried over anhydrous MgSO4,
concentrated under reduced pressure. The residue was purified
by column chromatography on silica gel (EtOAc in petroleum
ether) to afford the pure product 6. White solid; 245 mg, 82%
A mixture of boronic acid (1 mmol), anthranilamide (1 mmol),
Et3N (0.5 mmol) NiBr2(PPh3)2 (0.05 mmol), PdCl2 (0.05 mmol)
in EtOH (2 ml) was stirred at room temperature. The reaction
progress was monitored by thin-layer chromatography (TLC).
Upon completion, water (10 ml) was added and the solid
precipitate was filtered and purified by recrystallized from
ethanol/water or by column chromatography (silica gel, 5:1
petroleum ether/ethyl acetate as an eluent) to give the desired
pure products.
°
Yield; mp: 282–283 C; IR (KBr): 3528, 1659, 1608, 1530,
1488, 1362, 1278, 825, 763 cmÀ 1; 1H NMR (DMSO-d6,
400 MHz): δ 9.70 (s, 1H), 9.31 (s, 1H), 8.08–8.02 (m, 3H), 7.97
(s, 1H), 7.77 (d, J=8.8 Hz, 1H), 7.59 (t, J=8.0 Hz, 1H), 7.50–
7.46 (m, 3H), 7.37 (d, J=8.0 Hz, 1H), 7.18-7.11 (m, 2H), 1.30
(s, 9H) ppm; 13C NMR (DMSO-d6, 100 MHz): δ 166.8, 153.6,
152.9, 146.0, 134.5, 133.7, 129.5, 128.4, 125.0, 124.6, 121.2,
119.2, 118.6, 35.0, 31.5 ppm; EI-MS: m/z=355 (M+H)+.
General Procedure for Synthesis of bis
(1,3,2-Benzodiazaborininones)
A mixture of 1,4-phenylenediboronic acid (1 mmol), anthranila-
mide (2 mmol), Et3N (1.0 mmol) NiBr2(PPh3)2 (0.10 mmol),
PdCl2 (0.10 mmol) in EtOH (4 ml) was stirred at room temper-
ature until the reaction was completed as monitored by TLC.
Water was added and the solid precipitate was filtered and
purified by recrystallized from ethanol/water to give the pure
product 5.
Acknowledgements
2,2’-(1,4-Phenylene)bis(2,3-dihydrobenzo[d][1,3,2]diazabori-
nin-4(1H)-one) (5a): White solid; 328 mg, 90% Yield; mp:
We would like to thank the Science and Technology Research
Foundation of Hebei Normal University (L2018Z06) and the
National Natural Science Foundation of China (No. 21272053)
for financial support.
°
>300 C; IR (KBr): 3404, 3304, 1652, 1619, 1539, 1487, 1365,
1
1271, 826, 760 cmÀ 1; H NMR (DMSO-d6, 400 MHz): δ 9.82
(s, 2H), 9.44 (s, 2H), 8.19 (s, 4H), 8.07 (d, J=6.8 Hz, 2H), 7.61
(t, J=7.2 Hz, 2H), 7.49 (d, J=8.0 Hz, 2H), 7.15 (t, J=7.6 Hz,
2H) ppm; 13C NMR (DMSO-d6, 100 MHz): δ 166.8, 145.9,
134.8, 133.9, 133.1, 128.4, 121.4, 119.3, 118.6 ppm; EI-MS:
m/z=366 (M+H)+.
References
[1] a) S. J. Baker, J. W. Tomsho, S. J. Benkovic, Chem. Soc.
chi, N. Kurikawa, S. Honzumi, Y. Yamamoto, D.
2,2’-(1,4-Phenylene)bis(7-methyl-2,3-dihydrobenzo[d][1,3,2]
diazaborinin-4(1H)-one) (5b): Brown solid; 338 mg, 86%
°
Yield; mp: >300 C; IR (KBr): 3414, 3320, 1648, 1602, 1548,
1
1482, 1366, 1273, 870, 824, 743 cmÀ 1; H NMR (DMSO-d6,
Adv. Synth. Catal. 2019, 361, 1–8
6
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