10.1002/adsc.201701368
Advanced Synthesis & Catalysis
1j (0.24 mmol) and 41.0 mg of diphenylphosphine oxide
2a (0.2 mmol); 1H NMR (CDCl3, 400 MHz): δ = 7.80–7.75
(m, 2H), 7.70–7.65 (m, 2H), 7.52–7.39 (m, 6H), 7.33–7.29
(m, 2H), 7.25–7.16 (m, 2H), 3.76–3.69 (m, 1H), 2.40–2.34
(m, 2H), 2.30–2.21 (m, 1H), 2.06–1.99 (m, 1H), 1.28–1.17
(m, 4H),0.95 (t, J = 7.6 Hz, 3H), 0.76 (t, J = 6.8 Hz, 3H).
(benzofuran-2-yl(cyclopropyl)methyl)diphenyl
phosphine oxide (3o): 36.3 mg (yield 49%), prepared
from 50.0 mg of 1o (0.27 mmol) and 40.2 mg of
diphenylphosphine oxide 2a (0.2 mmol); 1H NMR (CDCl3,
400 MHz): δ = 7.88–7.83 (m, 2H), 7.75–7.70 (m, 2H),
7.56–7.26 (m, 8H), 7.20–7.12 (m, 2H), 6.72 (d, J = 2.4 Hz,
1H), 3.25 (t, J = 10.4 Hz, 1H), 1.54–1.47 (m, 1H), 0.57–
0.52 (m, 1H), 0.48–0.41 (m, 1H), 0.34–0.28 (m, 1H), -
0.01– -0.06 (m, 1H). 13C NMR (CDCl3, 100 MHz): δ =
154.3, 153.6 (d, JP-C = 2.8 Hz), 132.1 (d, JP-C = 96.0 Hz),
13C NMR (CDCl3, 100 MHz): δ = 154.2, 147.1 (d, JP-C
=
9.4 Hz), 131.8 (d, JP-C = 2.0 Hz), 131.6 (d, JP-C = 2.9 Hz),
131.5 (d, JP-C = 94.5 Hz), 131.4 (d, JP-C = 97.6 Hz), 131.38
(d, JP-C = 4.5 Hz), 131.29 (d, JP-C =4.9 Hz), 128.8 (d, JP-C
=
1.7 Hz), 128.5 (d, JP-C = 10.9 Hz), 128.1 (d, JP-C = 11.7 Hz), 132.0, 131.7 (d, JP-C = 2.3 Hz), 131.6 (d, JP-C = 3.3 Hz),
123.6, 122.1, 120.3 (d, JP-C = 7.9 Hz), 119.2, 111.1, 41.3 (d, 131.4 (d, JP-C = 8.8 Hz), 131.1 (d, JP-C = 8.6 Hz), 128.5 (d,
J = 67.2 Hz), 30.3 (d, JP-C = 12.8 Hz), 26.6, 22.1, 16.8,
13.84 (d, JP-C = 2.3 Hz), 13.77. 31P NMR (CDCl3, 162
MHz): δ = 31.9; HRMS (ESI-TOF): m/z = 417.1981, calcd
for C27H30O2P [MH+] 417.1983.
JP-C = 1.9 Hz), 128.3 (d, JP-C = 12.7 Hz), 128.2 (d, JP-C =
12.3 Hz), 123.6, 122.5, 120.7, 110.8, 105.6 (d, JP-C = 5.2
Hz), 45.8 (d, JP-C = 68.0 Hz), 10.1, 6.39 (d, JP-C = 1.4 Hz),
4.0 (d, JP-C = 10.0 Hz). 31P NMR (CDCl3, 162 MHz): δ =
30.5; HRMS (ESI-TOF): m/z = 373.1354, calcd for
C24H22O2P [MH+] 373.1357.
(E)-diphenyl((3-styrylbenzofuran-2-yl)methyl)
phosphine oxide (3k): 32.4 mg (yield 37%), prepared
from 60.4 mg of 1k (0.24 mmol) and 40.8 mg of
diphenylphosphine oxide 2a (0.2 mmol); 1H NMR (CDCl3,
400 MHz): δ = 7.82–7.74 (m, 5H), 7.50–7.32 (m, 11H),
7.27–7.23 (m, 3H), 7.05 (d, J = 16.0 Hz, 1H), 7.12 (dd, J1
(benzofuran-2-ylmethyl)di-o-tolylphosphine oxide (3q):
51.2 mg (yield 71%), prepared from 35.6 mg of 1a (0.24
1
mmol) and 46.0 mg of 2b (0.2 mmol); H NMR (CDCl3,
400 MHz): δ = 7.71–7.66 (m, 2H), 7.43–7.38 (m, 3H), 7.31
(d, J = 8.0 Hz, 1H), 7.25–7.12 (m, 6H), 6.59 (dd, J1 = 3.0
Hz, J2 = 0.6 Hz, 1H), 3.97 (d, J = 14.0 Hz, 2H), 2.35 (s,
6H). 13C NMR (CDCl3, 100 MHz): δ = 154.6, 148.8 (d, JP-
= 6.5 Hz), 142.0 (d, JP-C = 8.4 Hz), 131.96 (d, JP-C = 3.5
CHz), 131.89 (d, JP-C =11.3 Hz), 131.72 (d, JP-C = 11.1 Hz),
130.7 (d, JP-C = 98.1 Hz), 128.7 (d, JP-C = 2.3 Hz), 125.6 (d,
= 16.0 Hz, J2 = 1.2 Hz, 1H), 4.02 (d, J = 14.8 Hz, 2H). 13
C
NMR (CDCl3, 100 MHz): δ = 154.5, 146.9 (d, JP-C = 11.5
Hz), 137.5, 132.2 (d, JP-C = 2.5 Hz), 132.6 (d, JP-C = 99.7
Hz), 131.2 (d, JP-C = 9.5 Hz), 129.9 (d, JP-C = 3.9 Hz),
128.6 (d, JP-C = 4.3 Hz), 128.5, 127.4, 126.5 (d, JP-C = 2.4
Hz), 126.2, 124.3, 123.0, 120.5, 118.2 (d, J = 3.6 Hz),
117.0 (d, JP-C = 8.0 Hz), 111.2, 31.5 (d, JP-C = 66.4 Hz). 31
P
JP-C = 12.3 Hz), 123.6, 122.6, 120.6, 110.7, 106.2 (d, JP-C =
NMR (CDCl3, 162 MHz): δ = 28.1; HRMS (ESI-TOF):
m/z =435.1518, calcd for C29H24O2P [MH+] 435.1514.
(benzofuran-2-yl(phenyl)methyl)diphenylphosphine
oxide (3l): 48.0 mg (yield 58%), prepared from 58.0 mg of
1l (0.26 mmol) and 40.8 mg of diphenylphosphine oxide
2a (0.2 mmol); 1H NMR (CDCl3, 400 MHz): δ = 7.86–7.82
(m, 2H), 7.51–7.25 (m, 12H), 7.18–7.08 (m, 6H), 5.04 (d, J
= 10.8 Hz, 1H). 13C NMR (CDCl3, 100 MHz): δ = 154.4,
153.0, 133.4 (d, JP-C = 5.5 Hz), 132.0 (d, JP-C = 2.5 Hz),
5.6 Hz), 31.2 (d, JP-C = 67.3 Hz), 21.2 (d, JP-C = 4.9 Hz).
31P NMR (CDCl3, 162 MHz): δ = 30.5. HRMS (ESI-TOF):
m/z = 361.1355, calcd for C23H22O2P [MH+] 361.1357.
(benzofuran-2-ylmethyl)di-p-tolylphosphine oxide (3r):
57.6 mg (yield 80%), prepared from 35.6 mg of 1a (0.24
1
mmol) and 46.1 mg of 2c (0.2 mmol); H NMR (CDCl3,
400 MHz): δ = 7.64 (d, J = 8.0 Hz, 2H), 7.61 (d, J = 8.0 Hz,
2H), 7.43 (d, J = 7.2 Hz, 1H), 7.32 (d, J = 8.0 Hz, 1H),
7.27–7.24 (m, 4H), 7.20–7.12 (m, 2H), 6.53 (d, J = 3.2 Hz,
131.7 (d, JP-C = 3.4 Hz), 131.6 (d, JP-C = 98.4 Hz), 131.5 (d, 1H), 3.84 (d, J = 14.4 Hz, 2H), 2.39 (s, 6H). 13C NMR
JP-C = 101.0 Hz), 131.3 (d, JP-C = 1.5 Hz), 131.2 (d, JP-C
1.4 Hz), 129.9 (d, JP-C = 5.2 Hz), 128.7,128.6 (d, JP-C
=
=
(CDCl3, 100 MHz): δ = 154.6, 148.9 (d, JP-C = 7.3 Hz),
142.5 (d, JP-C = 2.6 Hz), 131.1 (d, JP-C = 9.8 Hz), 129.3 (d,
11.6 Hz), 128.4 (d, JP-C = 1.9 Hz), 128.2 (d, JP-C = 12.3 Hz), JP-C = 12.4 Hz), 128.8 (d, JP-C = 104.0 Hz), 128.7 (d, JP-C
=
127.5 (d, JP-C = 2.4 Hz), 123.9, 122.7, 121.1, 110.9, 106.7
(d, JP-C = 2.6 Hz), 47.9 (d, J = 65.0 Hz). 31P NMR (CDCl3,
162 MHz): δ = 29.6. HRMS (ESI-TOF): m/z = 409.1362,
calcd for C27H22O2P [MH+]409.1357.
3.0 Hz), 123.6, 122.6, 120.6, 110.8, 105.9 (d, JP-C = 5.5
Hz), 31.9 (d, JP-C = 67.6 Hz), 21.6 (d, JP-C = 1.5 Hz). 31P
NMR (CDCl3, 162 MHz): δ = 28.2. HRMS (ESI-TOF):
m/z = 361.1360, calcd for C23H22O2P [MH+]361.1357.
(benzofuran-2-ylmethyl)bis(4-fluorophenyl)phosphine
oxide (3s): 65.0 mg (yield 88%), 35.7 mg of 1a (0.24
(benzofuran-2-yl(p-tolyl)methyl)diphenylphosphine
oxide (3m): 52.0 mg (yield 61%), prepared from 57.8 mg
of 1m (0.24 mmol) and 41.0 mg of diphenylphosphine
1
mmol) and 47.6 mg of 2d (0.2 mmol); H NMR (CDCl3,
1
oxide 2a (0.2 mmol); H NMR (CDCl3, 400 MHz): δ =
400 MHz): δ = 7.77–7.71 (m, 4H), 7.46–7.44 (m, 1H), 7.31
(d, J = 8.0 Hz, 1H), 7.23–7.14 (m, 6H), 6.53 (dd, J1= 3.2
Hz, J2= 0.4 Hz, 1H), 3.86 (d, J = 14.4 Hz, 2H). 13C NMR
7.84–7.79 (m, 2H), 7.54–7.37 (m, 7H), 7.33–7.21 (m, 5H),
7.18–7.10 (m, 2H), 7.03–6.98 (m, 3H), 5.03 (d, J = 10.8
Hz, 1H), 2.24 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ =
154.3, 153.2, 137.2 (d, JP-C = 2.3 Hz), 131.8 (d, JP-C = 2.9
(CDCl3, 100 MHz): δ = 165.2 (dd, JF-C = 252.5 Hz, JP-C
3.2 Hz), 154.6, 148.0 (d, JP-C = 8.3 Hz), 133.6 (dd, JP-C
=
=
Hz), 131.7 (d, JP-C = 100.0 Hz), 131.61 (d, JP-C = 100.0 Hz), 11.0 Hz, JF-C = 9.0 Hz), 128.4 (d, JP-C = 2.5 Hz), 127.5 (dd,
131.60 (d, JP-C = 2.5 Hz), 131.3 (d, JP-C = 3.5 Hz), 131.2 (d, JP-C = 103.1 Hz, JF-C = 3.3 Hz), 124.0, 122.8, 120.7, 116.1
JP-C = 3.7 Hz), 130.3 (d, JP-C = 5.0 Hz), 129.7 (d, JP-C = 5.0
Hz), 129.1 (d, JP-C = 1.9 Hz), 128.6 (d, JP-C = 1.4 Hz),
128.5 (d, JP-C = 11.7 Hz), 128.1 (d, JP-C = 12.3 Hz), 123.8,
122.6, 120.9, 110.8, 106.5 (d, JP-C = 3.1 Hz), 47.6 (d, J =
65.6 Hz), 21.0. 31P NMR (CDCl3, 162 MHz): δ = 29.5.
HRMS (ESI-TOF): m/z = 423.1516, calcd for C28H24O2P
[MH+] 423.1514.
(dd, JP-C = 21.4 Hz, JF-C = 13.1 Hz), 110.8, 106.3 (d, JP-C =
6.7 Hz), 32.2 (d, JP-C = 68.7 Hz). 31P NMR (CDCl3, 162
MHz): δ = 26.6. HRMS (ESI-TOF): m/z = 369.0858, calcd
for C21H16F2O2P [MH+] 369.0856.
(benzofuran-2-ylmethyl)bis(4-methoxyphenyl)
phosphine oxide (3t): 70.6 mg (yield 90%), prepared from
35.5 mg of 1a (0.24 mmol) and 52.4 mg of 2e (0.2 mmol);
1H NMR (CDCl3, 400 MHz): δ = 7.65 (dd, J1= 11.2 Hz,
J2= 8.8 Hz, 4H), 7.43 (d, J = 6.8 Hz, 1H), 7.32 (d, J = 8.0
Hz, 1H), 7.20–7.13 (m, 2H), 6.95 (dd, J1= 8.8 Hz, J2= 2.4
Hz, 4H), 6.50 (d, J = 2.8 Hz, 1H), 3.83 (s, 6H), 3.82 (d, J=
13.2 Hz, 2H). 13C NMR (CDCl3, 100 MHz): δ = 162.5 (d,
JP-C = 2.7 Hz), 154.6 (d, JP-C = 1.5 Hz), 149.1 (d, JP-C = 7.0
Hz), 133.0 (d, JP-C = 10.4 Hz), 128.7 (d, JP-C = 3.2 Hz),
123.6, 123.3 (d, JP-C = 107.5 Hz), 122.6, 120.6, 114.2 (d,
JP-C = 13.6 Hz), 110.8, 105.8 (d, JP-C = 6.5 Hz), 55.4, 32.3
(d, JP-C = 68.4 Hz). 31P NMR (CDCl3, 162 MHz): δ = 28.0.
HRMS (ESI-TOF): m/z = 393.1258, calcd for C23H22O4P
[MH+] 393.1256.
(1-(benzofuran-2-yl)pentyl)diphenylphosphine
oxide
(3n): 62.0 mg (yield 80%), prepared from 53.9 mg of 1n
(0.26 mmol) and 40.8 mg of diphenylphosphine oxide 2a
1
(0.2 mmol); H NMR (CDCl3, 400 MHz): δ = 7.87–7.82
(m, 2H), 7.64–7.37 (m, 7H), 7.32–7.27 (m, 3H), 7.20–7.14
(m, 2H), 6.59 (d, J = 3.2 Hz, 1H), 3.81 (td, J1 = 11.2 Hz, J2
= 3.2 Hz, 1H), 2.15–1.94 (m, 2H), 1.35–1.19 (m, 4H), 0.77
(t, J = 6.8 Hz, 3H). 13C NMR (CDCl3, 100 MHz): δ =
154.4 (d, JP-C = 1.6 Hz), 153.4 (d, JP-C = 5.8 Hz), 131.9 (d,
JP-C = 3.4 Hz), 131.7 (d, JP-C = 3.1 Hz), 131.6 (d, JP-C
=
95.7 Hz), 131.32 (d, JP-C = 6.5 Hz), 131.28 (d, JP-C = 98.6
Hz), 131.23 (d, JP-C = 9.7 Hz), 128.7 (d, JP-C = 11.2 Hz),
128.6 (d, JP-C = 3.4 Hz), 128.2 (d, JP-C = 11.7 Hz), 123.6,
122.6, 120.7, 110.9, 105.7 (d, JP-C = 6.8 Hz), 41.7 (d, J =
68.0 Hz), 30.2 (d, JP-C = 11.8 Hz), 27.7, 22.2, 13.8. 31P
NMR (CDCl3, 162 MHz): δ = 31.2; HRMS (ESI-TOF):
m/z = 389.1672, calcd for C25H26O2P [MH+] 389.1670.
(benzofuran-2-ylmethyl)bis(3-chlorophenyl)phosphine
oxide (3u): 60.0 mg (yield 75%), prepared from 35.7 mg
of 1a (0.24 mmol) and 54.2 mg of 2f (0.2 mmol); 1H NMR
(CDCl3, 400 MHz): δ = 7.78–7.74 (m, 2H), 7.65–7.59 (m,
2H), 7.54–7.51 (m, 2H), 7.46–7.39 (m, 3H), 7.33 (d, J =
7
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