The Journal of Organic Chemistry
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1
50
7
(
.52 (m, 2H); 13C{ H} NMR (75.5 MHz, CDCl ) δ 172.4 (C), 134.0
2-Chloroanisole (7p). Boronic acid (0.20 mmol, 1.0 equiv),
PPh AuNTf (2:1 toluene adduct, 7.4 mg, 5 mol %), H O (40 μL, 2.0
3
CH), 130.4 (CH), 129.5 (C), 128.6 (CH).
Methyl Benzoate (7k). Boronic acid (0.28 mmol, 1.0 equiv),
PPh AuNTf (2:1 toluene adduct, 11 mg, 5 mol %), dimethylcarbonate
1.1 mL, 0.25 M), and H O (50 μL, 2.8 mmol, 10 equiv) were added to
the microwave tube and heated at 90 °C for 1 h in the microwave. The
resulting mixture was passed through a silica plug, washed with ether,
and then concentrated. The product was purified by column
chromatography (49:1 then 9:1 pentane/ether) to yield product 7k as
3
2
2
45
mmol, 10 equiv), and dimethylcarbonate (0.8 mL, 0.25 M) were added
to the microwave tube and heated at 90 °C for 1 h in the microwave. The
resulting mixture was passed through a silica plug, washed with ether,
and then concentrated. The product was purified by column
chromatography (7:1 pentane/ether) to yield product 7p as a colorless
oil (47%, 13.6 mg, 0.097 mmol): R 0.57 (5:1 pentane/ether); ν
3
2
(
2
f
max
−1
(cm ) 2940, 2838 (C−H), 1588, 1485, 1462, 1449 (Ar C−C), 1274
1
a colorless oil (89%, 34 mg, 0.25 mmol): R 0.7 (20:1 pentane/ether);
(C−O−C); H NMR (300 MHz, CDCl ) δ 7.37 (dd, 1H, J = 1.6, 7.8
f
3
−1
13
1
νmax/cm 3026, 2916, 2852 (C−H), 1725 (CO), 1492, 1451 (Ar C−
Hz), 7.20−7.25 (m, 1H), 6.87−6.95 (m, 2H), 3.90 (s, 3H); C{ H}
1
C), 1262 (C−O); H NMR (300 MHz, CD Cl ) δ 7.99−8.04 (m, 2H),
NMR (75.5 MHz, CDCl ) δ 155.1 (C), 130.4 (CH), 127.9 (CH), 122.6
2
2
3
13
1
7
.56 (tt, 1H, J = 1.4, 6.5 Hz), 7.41−7.48 (m, 2H), 3.88 (s, 3H); C{ H}
(C), 121.4 (CH), 112.2 (CH), 56.2 (CH ).
3
5
1
NMR: (75.5 MHz, CD Cl ) δ 167.4 (C), 133.4 (CH), 130.9 (C), 130.0
Bromobenzene (7q). Boronic acid (0.25 mmol, 1.0 equiv),
2
2
(
CH), 128.9 (CH), 52.5 (CH ).
Acetophenone (7l). Boronic acid (0.22 mmol, 1 equiv),
PPh AuNTf (2:1 toluene adduct, 9.8 mg, 5 mol %), dimethylcarbonate
3
3
2
4
6
(1.5 mL, 0.17 M), and H O (45 μL, 2.5 mmol, 10 equiv) were added to
2
PPh AuNTf (2:1 toluene adduct, 9 mg, 5 mol %), and dimethyl
the microwave tube and heated in the microwave at 90 °C for 1 h. The
resulting mixture was then passed through a silica plug, washed with
ether, and then concentrated. The product was purified by column
chromatography (20:1 pentane/ether) to yield product 7q as a colorless
liquid (47%, 18.3 mg, 0.102 mmol): R 0.65 (20:1 pentane/ether); ν
3
2
carbonate (0.8 mL) were added to the microwave tube and placed in the
microwave and heated at 90 °C for 2 h. A second portion of
PPh AuNTf (5 mol %) was then added to the reaction mixture, which
3
2
was then heated in the microwave for a further 2 h at 90 °C. The
resulting mixture was then passed through a silica plug and washed with
ether. The product was purified by column chromatography (7:1
pentane/ether) to yield product 7l as a colorless oil (65%, 17.2 mg, 0.14
f
max
−1
1
(cm ) 3064 (C−H), 1577, 1473, 1442 (Ar C−C), 730 (C−Br); H
NMR (300 MHz, CDCl ) δ 7.54−7.59 (m, 2H), 7.26−7.39 (m, 3H);
3
13
1
C{ H} NMR (75.5 MHz, CDCl ) δ 131.6 (CH), 130.1 (CH), 127.0
3
−
1
mmol): R 0.52 (5:1 pentane/ether); ν (cm ) 3062 (C−H), 1682
(CH), 122.6 (C).
1,3,5-Trimethylbenzene (7s). Boronic acid (0.20 mmol, 1.0
f
max
1
52
(
CO), 1598, 1582, 1448 (Ar C−C); H NMR (300 MHz, CDCl ) δ
3
7
2
.94−7.98 (m, 2H), 7.57 (tt, 1H, J = 1.3, 6.3 Hz), 7.43−7.50 (m, 2H),
equiv), PPh AuNTf (2:1 toluene adduct, 7.4 mg, 5 mol %), H O (40
3
2
2
.61 (s, 3H); 13C{ H} NMR (75.5 MHz, CDCl ) δ 198.3 (C), 137.3
1
3
μL, 10 equiv), and THF-d (0.8 mL, 0.25 M) were added to the
8
(
C), 133.2 (CH), 128.7 (CH), 128.4 (CH), 26.7 (CH ).
Nitrobenzene (7m). Boronic acid (0.30 mmol, 1.0 equiv),
microwave tube and heated at 90 °C for 1 h in the microwave. Internal
3
4
7
standard dimethylsulfone (9.4 mg, 0.5 equiv) was added to the mixture.
1
PPh AuNTf (2:1 toluene adduct, 12 mg, 5 mol %), dimethylcarbonate
H NMR yield of 95% was obtained. Due to the volatile nature of the
3
2
1
(
1.2 mL, 0.25 M), and H O (54 μL, 3.0 mmol, 10 equiv) were added to
product, an isolated yield was not obtained: H NMR (300 MHz, THF-
2
the microwave tube and placed in the microwave at 90 °C for 1 h. The
resulting mixture was passed through a silica plug, washed with ether,
and then concentrated. The product was purified by column
chromatography (49:1 then 9:1 pentane/ether) to yield product 7m
d ) δ 6.24 (s, 3H), 1.72 (s, 9H).
Anthracene (7t). Boronic acid (0.23 mmol, 1.0 equiv),
8
5
3
PPh AuNTf (2:1 toluene adduct, 8.8 mg, 5 mol %), dimethylcarbonate
3
2
(1.5 mL, 0.15 M), and H O (41 μL, 2.3 mmol, 10 equiv) were added to
2
as a colorless oil (92%, 34 mg, 0.28 mmol): R 0.5 (9:1 pentane/ether);
the microwave tube and heated at 90 °C for 2 h in the microwave. The
resulting mixture was the passed through a silica plug and washed with
ether. The product was purified by column chromatography (40:1
pentane/ether) to yield product 7t as a yellow solid (99%, 40.2 mg,
0.226 mmol): R 0.62 (40:1 pentane/ether); mp 194−196 °C; ν
f
−
1
νmax (cm ) 3076, 2859 (C−H), 1518 (NO ), 1477 (Ar C−C), 1343
2
1
(
1
NO ); H NMR (300 MHz, CDCl ) δ 8.22−8.26 (m, 2H), 7.70 (tt,
2
3
13
1
H, J = 1.2, 6.7 Hz), 7.52−7.59 (m, 2H); C{ H} NMR (75.5 MHz,
CDCl ) δ 148.4 (C), 134.7 (CH), 129.4 (CH), 123.6 (CH).
3
f
max
4
8
−1
1
Methyl 3-Nitrobenzoate (7n). Boronic acid (0.22 mmol, 1.0
(cm ) 3049, 3024, 2921 (C−H), 1590, 1533, 1450 (Ar C−C); H
equiv), PPh AuNTf2 (2:1 toluene adduct, 9 mg, 5 mol %),
NMR (300 MHz, CDCl ) δ 8.44 (s, 2H), 8.00−8.06 (m, 4H), 7.46−
3
3
7.52 (m, 4H); 13C{ H} NMR (75.5 MHz, CDCl ) δ 131.8 (C), 128.3
1
dimethylcarbonate (0.88 mL, 0.25 M), and H O (40 μL, 3.0 mmol,
2
3
10 equiv) were added to the microwave tube and placed in the
(CH), 126.3 (CH), 125.5 (CH).
1,3,5-Trisopropylbenzene (7u). Boronic acid (0.20 mmol, 1.0
5
4
microwave at 90 °C for 1 h. The resulting mixture was passed through a
silica plug, washed with ether, and then concentrated. The product was
purified by column chromatography (49:1 then 9:1 pentane/ether) to
equiv), PPh AuNTf (2:1 toluene adduct, 7.4 mg, 5 mol %), H O (40
3
2
2
μL, 2.0 mmol, 10 equiv), and dimethylcarbonate (0.8 mL, 0.25 M) were
added to the microwave tube and heated at 90 °C for 3 h in the
microwave. The resulting mixture was passed through a silica plug,
washed with ether, and then concentrated. The product was purified by
column chromatography (pentane) to yield product 7u as a colorless oil
yield product 7n as a white solid (70%, 28 mg, 0.15 mmol): R 0.2 (9:1
f
−1
pentane/ether); mp 77−78 °C; ν (cm ) 2955 (C−H), 1726 (C
max
O), 1531 (NO ), 1480, 1442 (Ar C−C), 1349 (NO ), 1263 (C−O−C);
2
2
1
H NMR (300 MHz, CDCl ) δ 8.87−8.89 (m, 1H), 8.42 (ddd, 1H, J =
3
−1
1
(
.1, 2.3, 8.2 Hz), 8.37 (dt, 1H, J = 1.7, 7.7 Hz), 7.63−7.69 (m, 1H), 3.99
(99%, 37.8 mg, 0.18 mmol): R 0.86 (5:1 pentane/ether); ν (cm )
f max
s, 3H); 13C{ H} NMR (75.5 MHz, CDCl ) δ 165.1 (C), 148.5 (C),
1
1
2957 (C−H), 1599, 1465, 1381 (Ar C−C); H NMR (300 MHz,
3
1
(
36.4 (CH), 132.0 (C), 129.8 (CH), 127.6 (CH), 124.8 (CH), 53.0
CH3).
-Nitroanisole (7o). Boronic acid (0.25 mmol, 1.0 equiv),
PPh AuNTf (2:1 toluene adduct, 10 mg, 5 mol %), dimethylcarbonate
CDCl ) δ 6.96 (s, 3H), 2.92 (sept, 3H, J = 6.9 Hz), (d, 18H, J = 6.9 Hz);
3
13
1
C{ H} NMR (75.5 MHz, CDCl ) δ 148.8 (C), 122.2 (CH), 34.4
3
4
9
2
(CH), 24.3 (CH3).
Fluorocene (7v).
5
5
3
2
Boronic acid (0.12 mmol, 1.0 equiv),
(
1.5 mL, 0.16 M), and H O (42 μL, 2.5 mmol, 10 equiv) were added to
PPh AuNTf (2:1 toluene adduct, 4.7 mg, 5 mol %), dimethylcarbonate
2
3 2
the microwave tube and heated at 90 °C for 1 h in the microwave. The
resulting mixture was then passed through a silica plug, washed with
ether, and then concentrated. The product was purified by column
chromatography (3:1 pentane/ether) to yield product 7o as an oil (97%,
(0.75 mL, 0.15 M), and H O (21 μL, 1.2 mmol, 10 equiv) were added to
2
the microwave tube and heated in the microwave at 90 °C for 1 h. The
resulting mixture was then passed through a silica plug, washed with
ether, and then concentrated. The product was purified by column
chromatography (40:1 pentane/ether) to yield product 7v as a yellow
−1
3
2
7.7 mg, 0.246 mmol): R 0.30 (3:1 pentane/ether); ν (cm ) 2946,
f max
−
1
923, 2916, 2844 (C−H), 1582 (NO ), 1492, 1463, 1451, 1438 (Ar C−
solid (74%, 14.6 mg, 0.088 mmol): mp 116−118 °C; ν (cm ) 3024,
2
max
1
1
C), 1347 (NO ), 1276 (C−O−C); H NMR (300 MHz, CDCl ) δ 7.82
2917 (C−H), 1574, 1490, 1477, 1447 (Ar C−C) ; H NMR (300 MHz,
2
3
(
dd, 1H, J = 1.7, 8.1 Hz), 7.53 (ddd, 1H, J = 1.7, 7.4, 8.5 Hz), 7.09 (dd,
CDCl ) δ 7.81 (dt, 2H, J = 0.9, 7.3 Hz), 7.55−7.58 (m, 2H), 7.37−7.42
3
1
3
1
1
H, J = 1.1, 8.5 Hz), 7.02 (ddd, 1H, J = 1.1, 7.4, 8.1 Hz), 3.95 (s, 3H);
(m, 2H), 7.32 (td, 2H, J = 1.2, 7.3 Hz), 3.92 (s, 2H); C{ H} NMR
1
3
1
C{ H} NMR (75.5 MHz, CDCl ) δ 153.1 (C), 139.8 (C), 134.3
(75.5 MHz, CDCl ) δ 143.3 (C), 141.8 (C), 126.9 (CH), 126.8 (CH)
3
3
(
CH), 125.8 (CH), 120.4 (CH), 113.6 (CH), 56.6 (CH3).
125.2 (CH), 120.0 (CH), 37.1 (CH3).
G
J. Org. Chem. XXXX, XXX, XXX−XXX