S. Liao, X. Hu, Y. Li et al.
Tetrahedron xxx (xxxx) xxx
diazaborinine (3e). White solid, White solid, m.p.92e93 C; 1
NMR (600 MHz, DMSO‑d
ꢀ
H
129.20, 127.73, 127.01, 119.14, 115.73, 104.96, 20.87.
2-(3,5-dimethylphenyl)-2,3-dihydro-1H-naphtho[1,8-de]
6
)
d
8.24 (s, 2H), 7.88 (d, J ¼ 7.8 Hz, 2H), 7.29
ꢀ
1
(
(
d, J ¼ 7.6 Hz, 2H), 7.10 (t, J ¼ 7.8 Hz, 2H), 6.91 (d, J ¼ 8.2 Hz, 2H), 6.62
[1,3,2] diazaborinine(3n). White solid, m.p.160.1e162 C H NMR
(600 MHz, DMSO‑d
8.21 (s, 2H), 7.55 (s, 2H), 7.08 (d, J ¼ 7.5 Hz,
3H), 6.90 (d, J ¼ 8.2 Hz, 2H), 6.61 (d, J ¼ 7.4 Hz, 2H), 2.34 (s, 6H).
NMR (151 MHz, DMSO‑d 142.95, 136.83, 136.43, 131.83, 130.87,
13
d, J ¼ 7.4 Hz, 2H), 2.66 (q, J ¼ 7.6 Hz, 2H), 1.22 (t, J ¼ 7.6 Hz, 3H).
146.24, 142.91, 136.42, 133.26, 128.10,
27.59,120.10, 116.60, 106.06, 28.76, 16.00.
-(4-isopropylphenyl)-2,3-dihydro-1H-naphtho[1,8-de]
C
6
) d
1
3
NMR (151 MHz, DMSO‑d
6
)
d
C
1
6
) d
2
128.11, 120.16, 116.59, 106.04, 21.53.
[
1,3,2] diazaborinine (3f). White solid, m.p.104e106 C; 1H NMR
600 MHz, DMSO‑d
8.22 (s, 2H), 7.88 (s, 2H), 7.31 (d, J ¼ 7.5 Hz,
H), 7.09 (tt, J ¼ 7.3, 3.4 Hz, 2H), 6.91 (dd, J ¼ 7.5, 3.1 Hz, 2H), 6.61 (q,
ꢀ
2-(3,5-dichlorophenyl)-2,3-dihydro-1H-naphtho[1,8-de]
[1,3,2] diazaborinine(3o). Yellow solid, m.p.189e191 C; 1H NMR
ꢀ
(
6
) d
2
(600 MHz, DMSO‑d
6
)
d
8.44 (s, 2H), 7.99 (d, J ¼ 2.0 Hz, 2H), 7.69 (d,
13
J ¼ 7.5, 6.9 Hz, 2H), 2.92 (p, J ¼ 6.8 Hz,1H),1.24 (d, J ¼ 6.9 Hz, 6H).
NMR (151 MHz, DMSO‑d 150.83, 142.92, 136.43, 133.27, 128.09,
26.10, 120.11, 116.60, 106.06, 34.01, 24.29.
-(4-bromophenyl)-2,3-dihydro-1H-naphtho[1,8-de] [1,3,2]
C
J ¼ 2.2 Hz,1H), 7.10 (t, J ¼ 7.7 Hz, 2H), 6.93 (d, J ¼ 8.1 Hz, 2H), 6.58 (d,
13
6
)
d
J ¼ 7.3 Hz, 2H). C NMR (151 MHz, DMSO‑d 142.39, 136.37,
6
) d
1
134.54, 131.47, 129.75, 128.16, 120.34, 117.12, 106.30.
2-(thiophen-2-yl)-2,3-dihydro-1H-naphtho[1,8-de]
2
[1,3,2]
diazaborinine(3r). White solid, m.p.89.7e90.2 C; 1H NMR
(600 MHz, DMSO‑d 8.24 (s, 2H), 7.87e7.73 (m, 2H), 7.30e7.22
(m, 1H), 7.08 (t, J ¼ 7.8 Hz,2H), 6.91 (d, J ¼ 8.0 Hz, 2H), 6.59 (d,
ꢀ
ꢀ
diazaborinine(3g). White solid, m.p.144.5e145.2 C; 1H NMR
600 MHz, DMSO‑d
(
6
)
d
8.33 (s, 2H), 7.90 (d, J ¼ 8.1 Hz, 2H),
6
) d
7
6
.72e7.58 (m, 2H), 7.09 (t, J ¼ 7.8 Hz, 2H), 6.92 (d, J ¼ 8.2 Hz, 2H),
13
13
.59 (d, J ¼ 7.3 Hz, 2H). C NMR (151 MHz, DMSO‑d
36.39, 135.26, 131.09, 128.12, 124.46, 120.19, 116.85, 106.18.
-(4-chlorophenyl)-2,3-dihydro-1H-naphtho[1,8-de] [1,3,2]
6
)
d
142.64,
J ¼ 7.3 Hz, 2H). C NMR (151 MHz, DMSO‑d
6
) d 142.54, 136.37,
1
135.17, 131.54, 128.77, 128.08, 120.02, 116.82, 106.16.
2
E)-2-styryl-2,3-dihydro-1H-naphtho[1,8-de]
[1,3,2]
dia-
diazaborinine(3h). Yellowish solid,148.5e150.6 C; 1H NMR
600 MHz, DMSO‑d
8.33 (s, 2H), 7.97 (dd, J ¼ 8.2, 1.5 Hz, 2H),
.58e7.47 (m, 2H), 7.14e7.03 (m, 2H), 6.92 (d, J ¼ 8.1 Hz, 2H), 6.59
ꢀ
zaborinine(3s). White solid, m.p.129.2e131 C; H NMR (600 MHz,
DMSO‑d
ꢀ
1
(
6
)
d
6
)
d
8.28 (s, 2H), 7.98e7.90 (m, 2H), 7.54 (d, J ¼ 7.9 Hz, 2H),
7
(
7.09 (t, J ¼ 7.8 Hz, 2H), 6.91 (d, J ¼ 8.5 Hz, 2H), 6.79 (dd, J ¼ 17.8,
13
d, J ¼ 7.4 Hz, 2H). C NMR (151 MHz, DMSO‑d
35.48, 135.03, 128.18, 128.11, 120.17, 116.84, 106.17. B NMR
193 MHz, Chloroform-d) 28.94.
-(3-chlorophenyl)-2,3-dihydro-1H-naphtho[1,8-de] [1,3,2]
6
) d 142.65, 136.39,
11.0 Hz, 1H), 6.61 (dd, J ¼ 7.5, 2.4 Hz, 2H), 5.94 (dd, J ¼ 17.4, 3.8 Hz,
11
1
1H), 5.33 (d, J ¼ 11.1 Hz, 1H). 13C NMR (151 MHz, DMSO‑d
6
)
(
d
d 142.82, 139.04, 137.15, 136.42, 133.47, 128.11, 125.87, 120.15, 116.70,
11
11
2
115.43, 106.11. B NMR (193 MHz, Chloroform-d)
(193 MHz, Chloroform-d) 29.14.
d 29.14. B NMR
ꢀ
1
diazaborinine(3i). Green solid, m.p.119.2e120.3 C; H NMR
600 MHz, DMSO‑d
d
(
6
)
d
8.38 (s, 2H), 8.02 (s, 1H), 7.90 (d, J ¼ 7.2 Hz,
2-(naphthalen-1-yl)-2,3-dihydro-1H-naphtho[1,8-de] [1,3,2]
diazaborinine(3t)
1
2
H), 7.56e7.42 (m, 2H), 7.10 (t, J ¼ 7.8 Hz, 2H), 6.93 (d, J ¼ 8.2 Hz,
13
ꢀ
1
H), 6.60 (d, J ¼ 7.4 Hz, 2H). C NMR (151 MHz, DMSO‑d
36.39, 133.64, 132.70, 131.64, 130.25, 130.15, 128.13, 120.26, 116.92,
06.22.
-(2-chlorophenyl)-2,3-dihydro-1H-naphtho [1,8-de] [1,3,2]
6
)
d
142.61,
Grey solid, m.p.140e143 C; H NMR (600 MHz, DMSO‑d ) d 8.33
6
1
1
(d, J ¼ 11.4 Hz, 2H), 8.12 (t, J ¼ 9.8 Hz,1H), 7.96 (t, J ¼ 7.6 Hz, 2H), 7.71
(t, J ¼ 7.7 Hz, 1H), 7.54 (p, J ¼ 7.3, 6.7 Hz, 3H), 7.08 (q, J ¼ 7.5 Hz, 2H),
13
2
6.93 (t, J ¼ 7.9 Hz, 2H), 6.56e6.48 (m, 2H). C NMR (151 MHz,
ꢀ
1
diazaborinine(3j). White solid, m.p.86e88 C; H NMR (600 MHz,
DMSO‑d
6
DMSO‑d ) d 142.94, 136.51, 135.68, 133.25, 131.39, 129.16, 128.93,
6
)
d
8.18 (s, 2H), 7.56 (dd, J ¼ 7.2, 1.6 Hz, 1H), 7.50e7.43 (m,
128.81, 128.11, 126.33, 126.09, 125.78, 120.31, 116.76, 106.06.
2
2
H), 7.46e7.36 (m, 1H), 7.07 (t, J ¼ 7.8 Hz, 2H), 6.92 (d, J ¼ 8.1 Hz,
2-methyl-2,3-dihydro-1H-naphtho[1,8-de] [1,3,2] diazabor-
13
ꢀ
1
H), 6.48 (d, J ¼ 7.3 Hz, 2H). C NMR (151 MHz, DMSO‑d
37.15, 136.45, 134.91, 131.12, 129.06, 128.09, 126.85, 120.28, 116.84,
06.09.
-(4-fluorophenyl)-2,3-dihydro-1H-naphtho[1,8-de] [1,3,2]
diazaborinine(3k). White solid, m.p.133.0e133.8; 1H NMR
600 MHz, DMSO‑d
6
)
d
142.65,
inine(3u). Pink solid, m.p.97e99 C; H NMR (600 MHz, DMSO‑d
6
)
1
1
d
7.99 (s, 2H), 7.20 (t, J ¼ 7.8 Hz, 2H), 7.02 (d, J ¼ 8.2 Hz, 2H), 6.53 (dd,
13
J ¼ 7.7, 3.3 Hz, 2H), 0.48 (s, 3H). C NMR (151 MHz, DMSO‑d
6
)
11
2
d
143.48, 137.04, 128.62, 120.32, 116.73, 105.81. B NMR (193 MHz,
Chloroform-d) 31.49.
2-ethyl-2.3-dihydro-1H-naphtho[1,8-de] [1,3,2] diazabor-
d
(
6
)
d
8.35e8.27 (m, 2H), 8.02 (ddq, J ¼ 8.6, 4.4,
1
2
6
.3 Hz, 2H), 7.29 (td, J ¼ 8.9, 2.1 Hz, 2H), 7.13e7.07 (m, 2H),
inine (3v). Grey liquid; H NMR (600 MHz, DMSO‑d
6
) d 7.71 (s, 2H),
13
.95e6.89 (m, 2H), 6.63e6.58 (m, 2H). C NMR (151 MHz,
164.97, 163.33, 142.73, 136.40, 135.58, 135.53, 128.11,
20.09, 116.77, 115.15, 115.02, 106.13.
-(4-(trifuoromethyl)phenyl)-2,3-dihydro-1H-naphtho[1,8-
7.03 (t, J ¼ 7.8 Hz, 2H), 6.84 (d, J ¼ 8.2 Hz, 2H), 6.41 (d, J ¼ 7.4 Hz, 2H),
13
DMSO‑d
6
)
d
1.02 (t, J ¼ 8.0 Hz, 3H), 0.81 (q, J ¼ 8.0 Hz, 2H). C NMR (151 MHz,
DMSO‑d 142.92, 136.46, 128.03, 119.87, 116.21, 105.44, 9.38.
2-cyclopropyl-2,3-dihydro-1H-naphtho[1,8-de] [1,3,2] dia-
1
6
) d
2
ꢀ
1
ꢀ
1
de][1,3,2]diazaborinine(3l). White solid, m.p.129e131 C; H NMR
600 MHz, DMSO‑d
8.44 (s, 2H), 8.16 (d, J ¼ 7.9 Hz, 2H), 7.81 (d,
J ¼ 8.0 Hz, 2H), 7.17e7.05 (m, 2H), 6.94 (d, J ¼ 8.2 Hz, 2H), 6.62 (d,
zaborinine (3w). White solid, m.p.60.2e61.3 C;
(600 MHz, DMSO‑d
H NMR
(
6
)
d
6
)
d
7.55 (s, 2H), 7.01 (t, J ¼ 7.8 Hz, 2H), 6.82 (d,
J ¼ 8.1 Hz, 2H), 6.37 (d, J ¼ 7.4 Hz, 2H), 0.62 (dt, J ¼ 9.2, 2.6 Hz, 2H),
13
13
J ¼ 7.4 Hz, 2H). C NMR (151 MHz, DMSO‑d
33.83, 130.57 (q, J ¼ 31.5 Hz), 128.13, 124.63 (q, J ¼ 3.2 Hz), 120.35,
17.01, 106.30.
6
)
d
142.56, 136.41,
0.55 (dd, J ¼ 6.2, 2.5 Hz, 2H), ꢁ0.10 (tt, J ¼ 9.4, 6.3 Hz, 1H). C NMR
1
1
6
(151 MHz, DMSO‑d ) d 142.84, 136.40, 127.99, 119.64, 116.11, 105.35,
4.57.
2
-(3-chloro-5-methylphenyl)-2,3-dihydro-1H-naphtho[1,8-
2-isopropyl-2,3-dihydro-1H-naphtho[1,8-de] [1,3,2] dia-
zaborinine(3x). White solid, m.p.60.8e62.9 C; H NMR (600 MHz,
ꢀ
ꢀ
de] [1,3,2] diazaborinine (3m). White solid, m.p.163.5e164.2 C;
H NMR (600 MHz, DMSO‑d
1
6
)
d
8.14 (s, 2H), 7.43 (d, J ¼ 2.5 Hz, 1H),
DMSO‑d
6
)
d
7.60 (s, 2H), 7.02 (t, J ¼ 7.8 Hz, 2H), 6.83 (dd, J ¼ 8.3,
7
2
.33 (dd, J ¼ 8.2, 2.4 Hz,1H), 7.24 (d, J ¼ 8.1 Hz,1H), 7.06 (t, J ¼ 7.8 Hz,
1.4 Hz, 2H), 6.43 (dd, J ¼ 7.4, 3.0 Hz, 2H), 1.11 (d, J ¼ 7.7 Hz, 1H), 1.03
13
13
H), 6.91 (d, J ¼ 8.3 Hz, 2H), 6.46 (d, J ¼ 7.4 Hz, 2H), 2.43 (s, 3H).
C
(d, J ¼ 6.8 Hz, 6H). C NMR (151 MHz, DMSO‑d
6
) d 142.93, 136.40,
NMR (151 MHz, DMSO‑d
6
)
d
141.61, 138.82, 135.36, 131.43, 130.49,
128.01, 119.88, 116.22, 105.60, 19.70.
7