Dalton Transactions
Paper
1
3
C NMR (100 MHz, CDCl
34.72; IR (neat): ν
3
): δ 24.87, 83.75, 127.69, 131.23,
2983, 1604, 1437, 1350, 1137, 1092, 857, benzene (2g). Yield: 95%. H NMR (400 MHz, CDCl ): δ 1.33
1,2-Dichloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-
1
1
7
max
3
−
1
05, 657 cm
;
ESI-HRMS m/z calcd for
): 222.1662; found: 222.1664.
Methyl (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzo- δ 25.15, 84.64, 130.29, 132.53, 134.04, 135.77, 136.83; IR (solu-
C
12
H
21BNO
2
(s, 12H), 7.43 (d, J = 8.0 Hz, 1H), 7.59 (dd, J = 1.2 Hz, 8.0 Hz,
+
13
(M + NH
4
3
1H), 7.86 (d, J = 1.6 Hz, 1H); C NMR (100 MHz, CDCl ):
1
ate (2b). Yield: 86% (p-isomer–m-isomer = 53 : 47). H NMR tion): νmax 2976, 1588, 1477, 1382, 1342, 1144, 1085, 1040,
): δ (m-isomer) 1.36 (s, 12H), 3.91 (s, 3H), 7.44 960 cm− ; ESI-HRMS m/z calcd for C12
1
H19BNCl O (M + NH ):
+
(400 MHz, CDCl
3
2
2
4
(t, J = 8.0 Hz, 1H), 7.98 (d, J = 7.6 Hz, 1H), 8.12 (d, J = 8.0 Hz, 290.0883; found: 290.0882.
1
H), 8.46 (s, 1H); (p-isomer) 1.36 (s, 12H), 3.92 (s, 3H), 7.86 (d,
1,3-Dichloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-
1
3
1
J = 8.4 Hz, 2H), 8.02 (d, J = 8.4 Hz, 2H); C NMR (100 MHz, benzene (2h). Yield: 94%. H NMR (400 MHz, CDCl
CDCl ): δ (p-isomer) 24.83, 52.10, 84.15, 128.52, 132.23, (s, 12H), 7.42 (t, J = 2.0 Hz, 1H), 7.64 (d, J = 2.0 Hz, 2H);
3
): δ 1.34
1
3
C
3
1
1
9
2
34.59, 167.10, (m-isomer) 24.83, 52.00, 84.06, 127.74, 129.47, NMR (100 MHz, CDCl
3
): δ 24.83, 84.48, 129.34, 131.04, 132.66,
35.76, 139.09, 167.07; IR (neat): νmax 2952, 1726, 1461, 1362, 134.68; IR (solution): νmax 2976, 1584, 1552, 1440, 1334, 144,
06 cm− ; ESI-HRMS m/z calcd for C H BNO (M + NH ): 966 cm ; ESI-HRMS m/z calcd for C H BNCl O (M + NH ):
1
+
−1
+
1
4
23
4
4
12 19
2
2
4
80.1717; found: 280.1719.
4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)(trifluoromethyl)-
290.0883; found: 290.0884.
1,3-Bis(trifluoromethyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxa-
borolan-2-yl)benzene (2i). Yield: 91%. H NMR (400 MHz,
(
1
1
benzene (2c). Yield: 91% (p-isomer–m-isomer = 31 : 69).
NMR (400 MHz, CDCl
H
1
3
3
, TMS): δ (m-isomer) 1.36 (s, 12H), 7.48 CDCl
3
): δ 1.37 (s, 12H), 7.94 (s, 1 H), 8.23 (s, 2H); C NMR
): δ 24.86, 84.83, 122.09, 124.66, 124.69,
(t, J = 7.6 Hz, 1H), 7.70 (d, J = 7.8 Hz, 1H), 7.97 (d, J = 7.6 Hz, (100 MHz, CDCl
3
1
9
1
H), 8.06 (s, 1H), (p-isomer) 1.36 (s, 12H), 7.61 (d, J = 8.1 Hz, 130.68, 131.02, 134.61; F NMR (376 MHz, CDCl ) δ −62.76;
3
1
3
−1
2
3
H), 7.91 (d, J = 7.8 Hz, 2H); C NMR (100 MHz, CDCl , TMS): IR (neat): νmax 2983, 1618, 1279, 1123, 849, 677 cm ;
+
6 2 4
δ (m-isomer) 24.85, 84.26, 124.29, 127.60, 127.99, 131.32, ESI-HRMS m/z calcd for C14H19BNF O (M + NH ): 358.1410;
1
37.96, (p-isomer) 24.53, 84.26, 124.15, 124. 29, 132.30, 134.96; found: 358.1408.
1
9
F NMR (376 MHz, CDCl
3
): δ (m-isomer) −62.93, (p-isomer)
2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene (2j).
1
−
9
62.51; IR (solution): νmax 2976, 1584, 1552, 1334, 1144, Yield: 92%. H NMR (400 MHz, CDCl , TMS): δ 1.35 (s, 12H),
3
66 cm− ; ESI-HRMS m/z calcd for C H BF NO (M + NH ): 7.19 (dd, J = 3.6 Hz, 4.4 Hz, 1H), 7.63 (d, J = 4.8 Hz, 1H), 7.64
1
+
1
3
20
3
2
4
1
3
2
50.1539; found: 250.1539.
4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)toluene
3
(d, J = 3.6 Hz, 1H); C NMR (100 MHz, CDCl , TMS): δ 24.76,
(
(2d). 84.07, 128.20, 132.34, 137.13; IR (neat): νmax 2966, 1519, 1423,
1
−1
Yield: 92% (p-isomer–m-isomer = 40 : 60). H NMR (400 MHz, 1358, 1132, 846 cm ; ESI-HRMS m/z calcd for C H BNO S
1
0
19
2
+
CDCl
3
): δ (m-isomer) 1.34 (s, 12H), 2.35 (s, 3H), 7.25–7.27 (m, (M + NH
H), 7.60 (t, J = 4.4 Hz, 1H), 7.63 (s, 1 H), (p-isomer) 1.34 (s, 5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-2-furancarb-
2H), 2.36 (s, 3H), 7.18 (d, J = 7.6 Hz, 2H), 7.70 (d, J = 7.6 Hz, oxylic acid methyl ester (2k). Yield: 93%. H NMR (400 MHz,
4
): 228.1224; found: 228.1224.
2
1
2
8
2
1
1
13
H); C NMR (100 MHz, CDCl
3 3
): δ (m-isomer) 21.27, 24.85, CDCl , TMS): δ (2-isomer) 1.35 (s, 12H), 3.89 (s, 3H), 7.07 (d,
3.71, 127.66, 131.73, 132.01, 135.29, 137.10, (p-isomer) 21.73, J = 3.6 Hz, 1H), 7.19 (d, J = 3.6 Hz, 1H), (3-isomer) 1.32 (s,
4.85, 83.60, 128.49, 134.76, 141.37; IR (solution): ν
611, 1461, 1358, 1089 cm ; ESI-HRMS m/z calcd for (100 MHz, CDCl
1
3
2960, 12H), 3.89 (s, 3H), 7.37 (s, 1H), 7.87 (s, 1H);
C-NMR
max
−
1
3
, TMS): δ (2-isomer) 24.70, 51.93, 84.70,
+
C
13
H
23BNO
2
(M + NH
4
): 236.1819; found: 236.1819.
117.86, 124.00, 148.29, 159.03; (3-isomer) 24.75, 51, 95, 83.91,
(
4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)anisole
(2e). 121.80, 123.9, 154.01, 159.07. 2 : 3 = 86/14; IR (neat): νmax 3112,
1
Yield: 87% (p-isomer–m-isomer = 49 : 51). H NMR (400 MHz, 2977, 1714, 1575, 1527, 1437, 1358, 1324, 1284, 1103,
): δ (m-isomer) 1.34 (s, 12H), 3.83 (s, 3H), 7.00 (dd, J = 780 cm− ; ESI-HRMS m/z calcd for C12
.8, 8.4 Hz, 1H), 7.29 (t, J = 8.0 Hz, 1H), 7.32 (d, J = 2.8 Hz, 1H), 270.1507; found: 270.1508.
.40 (d, J = 7.2 Hz, 1H), (p-isomer) 1.33 (s, 12H), 3.83 (s, 3H), 2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[b]thio-
1
+
CDCl
3
5 4
H21BNO (M + NH ):
2
7
6
1
3
1
3
.88 (d, J = 8.4 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H); C NMR phene (2l). Yield: 90%. H NMR (400 MHz, CDCl , TMS):
(
100 MHz, CDCl ): δ (m-isomer) 24.85, 55.23, 83.80, 117.90, δ 1.38 (s, 12H), 7.32–7.39 (m, 2H), 7.83–7.86 (m, 1H), 7.88 (s,
3
1
3
1
1
1
18.61, 127.14, 128.91, 158.97, (p-isomer) 24.85, 55.08, 83.53, 1H), 7.89–7.91 (m, 1H); C NMR (100 MHz, CDCl
3
, TMS):
13.27, 136.47, 162.08; IR (solution): νmax 2952, 1603, 1461, δ 24.81, 84.42, 122.49, 124.07, 124.34, 125.27, 134.46, 140.39,
−
1
382, 1354, 1093 cm ; ESI-HRMS m/z calcd for C H BNO
143.66; IR (neat): ν
2977, 1595, 1553, 1522, 135, 1120, 849,
1
3
23
3
max
+
−1
(
M + NH
4
): 252.1768; found: 252.1768.
-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-o-xylene (2f). (M + NH
753, 662 cm
;
ESI-HRMS m/z calcd for
): 278.1381; found: 278.1382.
2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzofuran
14 2
C H21BNO S
+
4
4
1
Yield: 60%. H NMR (400 MHz, CDCl ): δ 1.34 (s, 12H), 2.27 (s,
3
1
3
1
2
H), 2.28 (s, 3H), 7.14 (d, J = 7.6 Hz, 1H), 7.54 (d, J = 7.6 Hz, (2m). Yield: 92%. H NMR (400 MHz, CDCl
3
, TMS): δ
): δ 19.47, (2-isomer) 1.39 (s, 12H), 7.22 (t, J = 7.2 Hz, 1H), 7.33 (dt, J =
0.00, 24.83, 83.56, 129.13, 132.36, 135.88, 140.12; IR (solu- 1.2 Hz, 7.2 Hz, 1H), 7.40 (s, 1H), 7.56 (d, J = 8.4 Hz, 1H), 7.62
1
3
H), 7.58 (s, 1H); C NMR (100 MHz, CDCl
3
−
1
tion): νmax 2952, 1611, 1465, 1374, 1350, 1093 cm ; ESI-HRMS (d, J = 8.0 Hz, 1H), (3-isomer) 1.37 (s, 12H), 7.26–7.29 (m, 2H),
+
13
m/z calcd for C14
50.1975.
2 4 3
H25BNO (M + NH ): 250.1975; found: 7.91–7.93 (m, 2H), 7.95 (s, 1H); C NMR (100 MHz, CDCl ,
2
TMS): δ (2-isomer) 24.77, 84.66, 111.93, 119.51, 121.85, 122.70,
This journal is © The Royal Society of Chemistry 2015
Dalton Trans.