Page 5 of 6
The Journal of Organic Chemistry
MHz, Acetone-d6) δ 171.1, 160.6, 142.0, 137.0, 133.3, 128.8
(s, 3H). 13C{1H} NMR (400 MHz, Acetone-d6) δ 162.3, 160.5,
1
2
3
4
5
6
7
8
9
127.9, 127.0, 115.2, 55.6.
143.7, 134.2, 128.9, 115.0, 105.5, 99.4, 55.6.
N,N-diethyl-4'-methoxy-[1,1'-biphenyl]-3-amine (3g). 3g was
prepared from 1h (74 mg, 0.25 mmol) and 4-anisylB(pin) (117 mg,
4-fluoro-1,1'-biphenyl (3n).12 3n was prepared from phenyl
triflate 1a (57 mg, 0.25 mmol) and 4-fluorophenylboronic pinacol
ester (111 mg, 0.5 mmol, 2.0 equiv). The crude mixture was
purified by flash column chromatography (petroleum ether) to
0
.5 mmol, 2.0 equiv). The crude mixture was purified by flash
column chromatography (20% ethyl acetate/petroleum ether) to
afford the desired product as a white solid (42 mg, 65%). H NMR
1
1
afford the desired product as a white solid (26 mg, 60%). H NMR
(400 MHz, Acetone-d6) δ 7.54 (d, J = 8.8 Hz, 2H), 7.19 (dd, J =
(400 MHz, Acetone-d6) δ 7.75 – 7.66 (m, 2H), 7.65 – 7.56 (m, 2H),
7.53 – 7.42 (m, 2H), 7.40 – 7.32 (m, 1H), 7.22 (t, J = 8.9 Hz, 2H).
13C{1H} NMR (400 MHz, Acetone-d6) δ 162.4 (d, J = 244.5 Hz),
139.9, 137.3 (d, J = 3.2 Hz), 128.9, 128.7 (d, J = 8.1 Hz), 127.3,
126.8, 115.4 (d, J = 21.6 Hz).
8
1
.4, 7.5 Hz, 1H), 6.98 (d, J = 8.8 Hz, 2H), 6.87 (dd, J = 2.6, 1.7 Hz,
H), 6.79 (ddd, J = 7.5, 1.7, 0.9 Hz, 1H), 6.65 (ddd, J = 8.3, 2.7, 0.9
Hz, 1H), 3.83 (s, 3H), 3.44 (q, J = 7.0 Hz, 4H), 1.17 (t, J = 7.0 Hz,
1
3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
6H). C{1H} NMR (101 MHz, Acetone-d6) δ 160.2, 149.3, 142.7,
1
1
35.7, 130.5, 128.9, 115.0, 114.9, 114.8, 111.5, 111.1, 55.7, 45.1,
3.1. m/z HRMS (ESI) found [M+H]+ 256.1694, C17
21
3-fluoro-1,1'-biphenyl (3o). 3o was prepared from phenyl triflate
H
22NO
1
a (57 mg, 0.25 mmol) and 3-fluorophenylboronic pinacol ester
requires 256.1696.
-methoxy-1,1':3',1''-terphenyl (3h).18 3h was prepared from 1i
76 mg, 0.25 mmol) and 4-anisylB(pin) (117 mg, 0.5 mmol, 2.0
(111 mg, 0.5 mmol, 2.0 equiv). The crude mixture was purified by
4
flash column chromatography (petroleum ether) to afford the
desired product as a colourless oil (28 mg, 65%). H NMR (400
1
(
equiv). The crude mixture was purified by flash column
chromatography (2% dichloromethane/petroleum ether) to afford
the desired product as a white solid (61 mg, 94%). H NMR (400
MHz, Acetone-d6) δ 7.72 – 7.63 (m, 2H), 7.55 – 7.45 (m, 4H), 7.44
13
– 7.34 (m, 2H), 7.15 – 7.07 (m, 1H). C{1H} NMR (101 MHz,
1
Acetone-d6) δ 163.2 (d, J = 243.7 Hz), 143.4 (d, J = 7.7 Hz), 139.5
(d, J = 2.2 Hz), 130.6 (d, J = 8.5 Hz), 128.9, 127.9, 126.9, 122.7 (d,
J = 2.8 Hz), 113.8 (d, J = 21.2 Hz), 113.4 (d, J = 22.2 Hz).
MHz, Acetone-d6) δ 7.86 (t, J = 1.8 Hz, 1H), 7.78 – 7.72 (m, 2H),
7
7
3
1
1
.69 (d, J = 8.8 Hz, 2H), 7.59 (ddt, J = 7.4, 5.5, 1.5 Hz, 2H), 7.55 –
.45 (m, 3H), 7.43 – 7.33 (m, 1H), 7.05 (d, J = 8.8 Hz, 2H), 3.85 (s,
H). C{1H} NMR (101 MHz, Acetone-d6) δ 160.5, 142.5, 142.2,
42.0, 134.2, 130.2, 129.7, 129.0, 128.3, 127.9, 126.4, 126.2,
26.0, 115.2, 55.7.
-methoxy-1,1'-biphenyl (3p).22 3p was prepared from phenyl
3
1
3
triflate 1a (57 mg, 0.25 mmol) and 3-methoxyphenylboronic
pinacol ester (117 mg, 0.5 mmol, 2.0 equiv). The crude mixture was
purified
by
flash
column
chromatography
(5%
1
-(4-methoxyphenyl)naphthalene (3j).19 3j was prepared from 1k
69 mg, 0.25 mmol) and 4-anisylB(pin) (117 mg, 0.5 mmol, 2.0
dichloromethane/petroleum ether) to afford the desired product as
1
(
a white solid (30 mg, 64%). H NMR (400 MHz, Acetone-d6) δ
equiv). The crude mixture was purified by flash column
chromatography (0-5% dichloromethane /petroleum ether) to
afford the desired product as a white solid (42 mg, 72%). H NMR
7.74 – 7.63 (m, 2H), 7.47 (t, J = 7.5 Hz, 2H), 7.38 (m, 2H), 7.30 –
7.17 (m, 2H), 6.95 (ddd, J = 8.2, 2.5, 1.0 Hz, 1H), 3.88 (s, 1H).
1
13
C{1H} NMR (101 MHz, Acetone-d6) δ 160.2, 142.5, 140.9,
(400 MHz, CD
2
Cl
2
) δ 8.02 (s, 1H), 7.99 – 7.83 (m, 3H), 7.75 (dd, J
129.8, 128.8, 127.4, 126.9, 119.2, 112.8, 112.4, 54.7.
=
8.5, 1.9 Hz, 1H), 7.69 (d, J = 8.9 Hz, 2H), 7.49 (td, J = 7.3, 1.5
-Methyl-1,1'-biphenyl (3q).23 3q was prepared from phenyl
2
13
Hz, 2H), 7.04 (d, J = 8.9 Hz, 2H), 3.87 (s, 3H). C{1H} NMR (101
MHz, CD Cl ) δ 159.9, 138.5, 134.2, 133.8, 132.8, 128.7, 128.4,
128.0, 126.7, 126.1, 125.7, 125.2, 114.7, 55.7.
-(4-methoxyphenyl)naphthalene (3k).12 3k was prepared from 1l
triflate 1a (57 mg, 0.25 mmol) and 3-methoxyphenylboronic
pinacol ester (109 mg, 0.5 mmol, 2.0 equiv). The crude mixture was
purified by flash column chromatography (petroleum ether) to
2
2
1
1
afford the desired product as a colourless oil (25 mg, 59%). H
(69 mg, 0.25 mmol) and 4-anisylB(pin) (117 mg, 0.5 mmol, 2.0
equiv). The crude mixture was purified by flash column
chromatography (5-10% diethyl ether/petroleum ether) to afford
the desired product as a white solid (37 mg, 63%). H NMR (400
MHz, Acetone-d6) δ 7.96 (dd, J = 8.1, 1.5 Hz, 1H), 7.89 (ddt, J =
NMR (400 MHz, Acetone-d6) δ 7.48 – 7.41 (m, 2H), 7.39 – 7.15
1
3
(m, 7H), 2.24 (s, 3H). C{1H} NMR (101 MHz, Acetone-d6) δ
142.0, 141.9, 134.9, 130.2, 129.5, 129.0, 128.1, 127.2, 126.8,
125.8, 19.6.
1
8
3
.5, 2.1, 0.9 Hz, 2H), 7.61 – 7.35 (m, 6H), 7.09 (d, J = 8.8 Hz, 2H),
.88 (s, 3H). C{1H} NMR (101 MHz, Acetone-d6) δ 160.2,
ASSOCIATED CONTENT
13
Supporting Information
140.8, 135.0, 133.7, 132.7, 131.8, 129.2, 128.2, 127.7, 126.8,
126.6, 126.5, 126.3, 114.6, 55.6.
NMR spectra of 3a-3h and 3j-3q.
6-(4-methoxyphenyl)-1,2,3,4-tetrahydronaphthalene (3l). 3l was
prepared from 1m (70 mg, 0.25 mmol) and 4-anisylB(pin) (117 mg,
AUTHOR INFORMATION
0
.5 mmol, 2.0 equiv). The crude mixture was purified by flash
column chromatography (5-10% diethyl ether/petroleum ether) to
afford the desired product as a white solid (49 mg, 83%). H NMR
1
(
7
400 MHz, Acetone-d6) δ 7.53 (dd, J = 8.9, 2.3 Hz, 2H), 7.39 –
.21 (m, 2H), 7.07 (dd, J = 7.9, 2.0 Hz, 1H), 6.98 (dt, J = 8.9, 2.5
Hz, 2H), 3.81 (d, J = 2.3 Hz, 3H), 2.79 – 2.75 (m, 4H), 1.80 – 1.78
ORCID
Hung A. Duong: 0000-0003-0086-2463
1
3
(m, 4H). C{1H} NMR (101 MHz, Acetone-d6) δ 160.0, 138.7,
1
2
38.0, 136.2, 134.4, 130.3, 128.5, 127.8, 124.5, 115.0, 55.6, 30.1,
9.7, 24.1. m/z HRMS (ESI) found [M]+ 238.1354, C17H18O
Notes
The authors declare no competing financial interest.
requires 238.1352.
,4',5-trimethoxy-1,1'-biphenyl (3m).20 3m was prepared from 1n
72 mg, 0.25 mmol) and 4-anisylB(pin) (117 mg, 0.5 mmol, 2.0
3
ACKNOWLEDGMENTS
(
The financial support for this work was provided by “GSK-EDB
Singapore Partnership for Green and Sustainable Manufacturing”
and the Institute of Chemical and Engineering Sciences (ICES),
Agency for Science, Technology and Research (A*STAR),
Singapore.
equiv). The crude mixture was purified by flash column
chromatography (25-30% dichloromethane/petroleum ether) to
afford the desired product as a white solid (54 mg, 88%). H NMR
(400 MHz, Acetone-d6) δ 7.58 (d, J = 8.9 Hz, 2H), 6.99 (d, J = 8.8
Hz, 2H), 6.74 (d, J = 2.3 Hz, 2H), 6.45 (s, 1H), 3.84 (s, 6H), 3.83
1
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