10.1002/adsc.201700957
Advanced Synthesis & Catalysis
(0.13 mmol) and 20.2 mg of 2a (0.1 mmol) in 1 mL MeCN. HRMS (ESI-TOF): m/z = 449.2027, calcd for C31H30OP
1H NMR (CDCl3, 400 MHz): δ = 7.78–7.69 (m, 4H), 7.51–
7.38 (m, 3H), 7.35–7.32 (m, 2H), 7.27–7.24 (m, 2H), 7.21–
7.17 (m, 1H), 7.09 (d, J = 8.0 Hz, 2H), 6.11 (dt, J1 = 11.2
Hz, J2 = 3.2 Hz, 1H), 2.49–2.33 (m, 2H), 1.60–1.52 (m,
2H), 1.37–1.29 (m, 2H), 0.84 (t, J = 7.4 Hz, 3H). 31P NMR
(CDCl3, 162 MHz): δ = 29.5.
[MH+] 449.2034.
(1,1-Diphenylhepta-1,2-dien-3-yl)diphenylphosphine
oxide (3o). 18.2 mg (yield 20%), prepared from 63.4 mg of
1o (0.24 mmol) and 40.4 mg of 2a (0.2 mmol) in 2 mL
1
MeCN; 24.3 mg of 2a recovered. H NMR (CDCl3, 400
MHz): δ = 7.66–7.61 (m, 4H), 7.46–7.42 (m, 2H), 7.34–
7.26 (m, 10H), 6.99–6.97 (m, 4H), 2.47–2.41 (m, 2H),
1.67–1.59 (m, 2H), 1.35–1.31 (m, 2H), 0.83 (t, J = 7.4 Hz,
3H). 13C NMR (CDCl3, 100 MHz): δ = 208.8 (d, JP-C = 5.9
Hz), 135.3 (d, JP-C = 6.8 Hz), 131.79 (d, JP-C = 103.2 Hz),
131.76 (d, JP-C = 2.5 Hz), 131.5 (d, JP-C = 9.3 Hz), 128.4,
128.2 (d, JP-C = 12.0 Hz), 128.1 (d, JP-C = 2.5 Hz), 127.7,
112.7 (d, JP-C = 14.6 Hz), 102.0 (d, JP-C = 98.4 Hz), 30.6 (d,
JP-C = 5.9 Hz), 28.1 (d, JP-C = 7.4 Hz), 22.4, 13.8. 31P NMR
(CDCl3, 162 MHz): δ = 29.9. HRMS (ESI-TOF): m/z =
449.2038, calcd for C31H30OP [MH+] 449.2034.
(1-(4-Fluorophenyl)hepta-1,2-dien-3-yl)diphenyl
phosphine oxide (3j). 67.3 mg (yield 86%), prepared from
49.5 mg of 1j (0.24 mmol) and 40.4 mg of 2a (0.2 mmol)
1
in 2 mL MeCN. H NMR (CDCl3, 400 MHz): δ = 7.79–
7.74 (m, 2H), 7.71–7.65 (m, 2H), 7.52–7.50 (m, 1H), 7.46–
7.39 (m, 3H), 7.35–7.32 (m, 2H), 7.05–7.02 (m, 2H), 6.97–
6.92 (m, 2H), 6.09 (dt, J1 = 10.8 Hz, J2 = 3.2 Hz, 1H),
2.50–2.29 (m, 2H), 1.60–1.48 (m, 2H), 1.38–1.31 (m, 2H),
0.84 (t, J = 7.4 Hz, 3H). 13C NMR (CDCl3, 100 MHz): δ =
208.9 (dd, JP-C = 6.4 Hz, JF-C = 1.9 Hz), 162.1 (dd, JF-C
=
245.6 Hz, JP-C = 1.3 Hz), 131.71 (d, JP-C = 104.7 Hz),
131.9 (d, JP-C = 3.3 Hz), 131.8 (d, JP-C = 2.8 Hz), 131.6 (d,
(1-Cyclohexylidene-3,3-dimethylbut-1-en-2-yl)diphenyl
phosphine oxide (3p). 32.5 mg (yield 43%), prepared
from 43.2 mg of 1p (0.24 mmol) and 40.4 mg of 2a (0.2
mmol) in 2 mL MeCN; 12.8 mg of 2a recovered. 1H NMR
(CDCl3, 400 MHz): δ = 7.69–7.64 (m, 4H), 7.48–7.38 (m,
JP-C = 10.3 Hz), 131.4 (d, JP-C = 10.4 Hz), 131.3 (d, JP-C
=
104.7 Hz), 128.5 (dd, JF-C = 6.5 Hz, JP-C = 2.3 Hz), 128.3
(d, JP-C = 12.2 Hz), 128.1 (d, JP-C = 13.0 Hz), 128.0 (d, JF-C
= 7.9 Hz, JP-C = 2.0 Hz), 115.5 (d, JP-C = 21.8 Hz), 103.3 (d, 6H), 1.99–1.91 (m, 2H), 1.76–1.88 (m, 2H), 1.42–1.24 (m,
JP-C = 97.7 Hz), 96.4 (d, JP-C = 14.2 Hz), 30.4 (d, JP-C = 5.6
Hz), 27.8 (d, JP-C = 5.5 Hz), 22.3, 13.7. 31P NMR (CDCl3,
162 MHz): δ = 29.5. HRMS (ESI-TOF): m/z = 391.1616,
calcd for C25H25FOP [MH+] 391.1627.
4H), 1.20 (s, 9H), 1.09–1.00 (m, 2H). 13C NMR (CDCl3,
100 MHz): δ = 203.8 (d, JP-C = 8.8 Hz), 134.7 (d, JP-C
=
102.0 Hz), 131.4 (d, JP-C = 9.0 Hz), 131.0 (d, JP-C = 2.5 Hz),
127.9 (d, JP-C = 11.2 Hz), 105.2 (d, JP-C = 100.3 Hz), 104.5
(1-(2-Fluorophenyl)hepta-1,2-dien-3-yl)diphenyl
phosphine oxide (3k). 65.0 mg (yield 83%), prepared
from 49.4 mg of 1k (0.24 mmol) and 40.4 mg of 2a (0.2
(d, JP-C = 13.6 Hz), 36.2 (d, JP-C = 7.2 Hz), 30.8 (d, JP-C =
3.5 Hz), 30.1 (d, JP-C = 6.3 Hz), 26.3 (d, JP-C = 3.4 Hz),
25.4. 31P NMR (CDCl3, 162 MHz): δ = 31.6. HRMS (ESI-
TOF): m/z = 387.1860, calcd for C24H29OPNa [MNa+]
387.1854.
1
mmol) in 2 mL MeCN. H NMR (CDCl3, 400 MHz): δ =
7.78–7.68 (m, 4H), 7.50–7.46 (m, 1H), 7.42–7.38 (m, 3H),
7.35–7.30 (m, 2H), 7.17–7.08 (m, 2H), 7.04–6.93 (m, 2H),
(1-Cyclohexylidenehex-1-en-2-yl)diphenylphosphine
6.26 (dt, J1 = 11.2 Hz, J2 = 3.4 Hz, 1H), 2.48–2.29 (m, 2H), oxide (3q). 29.4 mg (yield 39%), prepared from 43.2 mg
1.59–1.52 (m, 2H), 1.38–1.29 (m, 2H), 0.83 (t, J = 7.4 Hz,
of 1q (0.24 mmol) and 40.4 mg of 2a (0.2 mmol) in 2 mL
MeCN; 16.2 mg of 2a recovered.. H NMR (CDCl3, 400
3H). 13C NMR (CDCl3, 100 MHz): δ = 209.6 (dd, JP-C
6.0 Hz, JF-C = 1.4 Hz), 159.4 (dd, JF-C = 248.6 Hz, JP-C
=
=
1
MHz): δ = 7.73–7.68 (m, 4H), 7.50–7.41 (m, 6H), 2.24–
2.19 (m, 2H), 2.01–1.93 (m, 2H), 1.85–1.80 (m, 2H), 1.47–
1.41 (m, 4H), 1.34–1.28 (m, 4H), 1.06–0.98 (m, 2H), 0.84
(t, J = 7.2 Hz, 3H). 13C NMR (CDCl3, 100 MHz): δ =
204.0 (d, JP-C = 7.6 Hz), 137.6 (d, JP-C = 102.8 Hz), 131.6
3.3 Hz), 131.86 (d, JP-C = 3.5 Hz), 131.80 (d, JP-C = 105.1
Hz), 131.74 (d, JP-C = 2.5 Hz), 131.53 (d, JP-C = 9.8 Hz),
131.42 (d, JP-C = 10.5 Hz), 131.40 (d, JP-C = 104.0 Hz),
128.7 (dd, JF-C = 8.0 Hz, JP-C = 1.5 Hz), 128.3 (d, JP-C
=
10.2 Hz), 128.13 (d, JP-C = 11.1 Hz), 128.12, 124.1 (d, JP-C
(d, JP-C = 8.7 Hz), 131.4 (d, JP-C = 2.5 Hz), 128.2 (d, JP-C =
= 3.2 Hz), 120.3 (d, JF-C = 12.1 Hz, JP-C = 7.2 Hz), 115.5 (d, 12.1 Hz), 104.8 (d, JP-C = 14.6 Hz), 96.3 (d, JP-C = 103.3
JP-C = 21.2 Hz), 102.8 (d, JP-C = 97.5 Hz), 96.0 (dd, JP-C
=
Hz), 30.4 (d, JP-C = 5.7 Hz), 30.1 (d, JP-C = 5.5 Hz), 27.2 (d,
JP-C = 7.9 Hz), 26.4 (d, JP-C = 3.3 Hz), 25.5, 22.1, 13.9. 31P
NMR (CDCl3, 162 MHz): δ = 32.1. HRMS (ESI-TOF):
m/z = 365.2016, calcd for C24H30OP [MH+] 365.2034.
(1,3-Diphenylpropa-1,2-dien-1-yl)diphenylphosphine
oxide (3r). [13a] 54.9 mg (yield 70%), prepared from 62.5
mg of 1r (0.3 mmol) and 40.4 mg of 2a (0.2 mmol) in 2
mL MeCN. 1H NMR (CDCl3, 400 MHz): δ = 7.80–7.72 (m,
4H), 7.68 (d, J = 8.0 Hz, 2H), 7.48–7.44 (m, 1H), 7.39–
7.21 (m, 11H), 7.12 (d, J = 7.6 Hz, 2H), 6.29 (d, J = 10.8
Hz, 1H). 31P NMR (CDCl3, 162 MHz): δ = 29.6.
13.8 Hz, JF-C = 5.8 Hz), 30.4 (d, JP-C = 5.0 Hz), 27.7 (d, JP-
= 6.3 Hz), 22.3, 13.7. 31P NMR (CDCl3, 162 MHz): δ =
C29.6. HRMS (ESI-TOF): m/z = 391.1618, calcd for
C25H25FOP [MH+] 391.1627.
Diphenyl(1-(4-(trifluoromethyl)phenyl)hepta-1,2-dien-
3-yl)phosphine oxide (3l). 64.3 mg (yield 73%), prepared
from 76.8 mg of 1l (0.3 mmol) and 40.4 mg of 2a (0.2
1
mmol) in 2 mL MeCN. H NMR (CDCl3, 400 MHz): δ =
7.79–7.66 (m, 4H), 7.54–7.40 (m, 6H), 7.52–7.50 (m, 1H),
7.36–7.31 (m, 2H), 7.16 (d, J = 8.4 Hz, 2H), 6.13 (dt, J1 =
9.2 Hz, J2 = 3.2 Hz, 1H), 2.52–2.32 (m, 2H), 1.59–1.50 (m,
2H), 1.37–1.32 (m, 2H), 0.84 (t, J = 7.4 Hz, 3H). 13C NMR
(CDCl3, 100 MHz): δ = 209.3 (d, JP-C = 6.4 Hz), 136.7 (d,
(1-Cyclopropyl-3-phenylpropa-1,2-dien-1-yl)diphenyl
phosphine oxide (3t). 83.4 mg (yield 78%), prepared from
61.9 mg of 1s (0.36 mmol) and 60.6 mg of 2a (0.3 mmol)
1
JP-C = 5.8 Hz), 132.08 (d, JP-C = 3.4 Hz), 131.93 (d, JP-C
=
in 3 mL MeCN. H NMR (CDCl3, 400 MHz): δ = 7.81–
2.7 Hz), 131.65 (d, JP-C = 105.0 Hz), 131.55 (d, JP-C = 9.2
Hz), 131.37 (d, JP-C = 9.3 Hz), 131.24 (d, JP-C = 103.4 Hz),
128.4 (d, JP-C = 12.0 Hz), 128.3 (d, JP-C = 12.21Hz), 126.7
(d, JP-C = 1.8 Hz), 126.0 (d, JF-C = 225.2 Hz), 125.5 (d, JP-C
= 2.9 Hz), 104.3 (d, JP-C = 96.7 Hz), 96.4 (d, JP-C = 13.0
Hz), 30.5 (d, JP-C = 5.2 Hz), 27.8 (d, JP-C = 5.9 Hz), 22.3,
13.7. 31P NMR (CDCl3, 162 MHz): δ = 29.6. HRMS (ESI-
TOF): m/z = 441.1591, calcd for C26H25F3OP [MH+]
441.1595.
(4,4-Dimethyl-1,1-diphenylpenta-1,2-dien-3-yl)diphenyl
phosphine oxide (3n). 16.4 mg (yield 18%), prepared
from 63.4 mg of 1n (0.24 mmol) and 40.4 mg of 2a (0.2
mmol) in 2 mL MeCN; 23.1 mg of 2a recovered. 1H NMR
(CDCl3, 400 MHz): δ = 7.61–7.56 (m, 4H), 7.40–7.36 (m,
2H), 7.28–7.25 (m, 10H), 6.97–6.94 (m, 4H), 1.35 (s, 9H).
13C NMR (CDCl3, 100 MHz): δ = 208.1 (d, JP-C = 7.5 Hz),
135.3 (d, JP-C = 7.0 Hz), 133.7 (d, JP-C = 103.4 Hz), 133.4
(d, JP-C = 8.2 Hz), 131.4 (d, JP-C = 9.7 Hz), 128.3, 128.0 (d,
JP-C = 14.1 Hz), 127.9, 127.6, 112.0 (d, JP-C = 14.8 Hz),
110.6 (d, JP-C = 93.5 Hz), 38.0 (d, JP-C = 5.9 Hz), 30.9 (d,
JP-C = 4.4 Hz). 31P NMR (CDCl3, 162 MHz): δ = 29.0.
7.73 (m, 4H), 7.51–7.48 (m, 1H), 7.43–7.32 (m, 5H), 7.27–
7.17 (m, 3H), 7.06 (d, J = 8.0 Hz, 2H), 6.16 (dd, J1 = 10.8
Hz, J2 = 1.6 Hz, 1H), 1.65–1.57 (m, 1H), 0.86–0.81 (m,
2H), 0.62–0.60 (m, 2H). 13C NMR (CDCl3, 100 MHz): δ =
207.2 (d, JP-C = 7.2 Hz), 132.6, 132.3 (d, JP-C = 6.7 Hz),
131.83 (d, JP-C = 2.7 Hz), 131.73 (d, JP-C = 4.2 Hz), 131.70
(d, JP-C = 103.9 Hz), 131.65 (d, JP-C = 10.2 Hz), 131.5 (d,
JP-C = 9.8 Hz), 128.6 (d, JP-C = 1.5 Hz), 128.2 (d, JP-C = 6.8
Hz), 128.1 (d, JP-C = 7.3 Hz), 127.5 (d, JP-C = 1.3 Hz),
126.6 (d, JP-C = 2.6 Hz), 107.4 (d, JP-C = 99.6 Hz), 99.0 (d,
JP-C = 13.3 Hz), 9.0 (d, JP-C = 18.4 Hz), 9.03, 8.9 (d, JP-C
=
1.5 Hz). 31P NMR (CDCl3, 162 MHz): δ = 29.8. HRMS
(ESI-TOF): m/z = 357.1395, calcd for C24H22OP [MH+]
357.1408.
(4,4-Dimethyl-1-phenylpenta-1,2-dien-3-yl)di-p-tolyl
phosphine oxide (3u). 65.4 mg (yield 82%), prepared
from 45.1 mg of 1a (0.24 mmol) and 45.9 mg of 2b (0.2
mmol) in 2 mL MeCN. 1H NMR (CDCl3, 400 MHz): δ =
7.62 (dd, J1 = 12.0 Hz, J2 = 8.0 Hz, 2H), 7.50 (dd, J1 = 12.0
Hz, J2 = 8.0 Hz, 2H), 7.22–7.16 (m, 5H), 7.01–7.98 (m,
4H), 6.00 (d, J = 11.2 Hz, 1H), 2.38 (s, 3H), 2.21 (s, 3H),
1.33 (s, 9H). 13C NMR (CDCl3, 100 MHz): δ = 208.9 (d,
7
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