The Journal of Organic Chemistry
Note
(1-Phenylethyl)triphenylphosphonium Bromide (2j).29 Yield:
3.56 g, 80%. All spectral data are consistent with those described
above.
[1-(4-Bromophenyl)ethyl]triphenylphosphonium Bromide (2k).
Yield: 4.10 g, 78%. All spectral data are consistent with those
described above.
{[5-(2-Fluorophenyl)furan-2-yl]methyl}triphenylphosphonium
1
Bromide (4e). Yield: 4.23 g, 82%; white solid, mp 258−260 °C; H
NMR (400 MHz, DMSO-d6): δ 7.99−7.87 (m, 3H), 7.85−7.71 (m,
12H), 7.38−7.21 (m, 2H), 7.19−7.09 (m, 1H), 7.96−7.86 (m, 1H),
6.78 (br s, 1H), 6.47 (t, J = 3.4 Hz, 1H), 5.60 (d, J = 15.0 Hz, 2H).
13C{1H} NMR (100 MHz, DMSO-d6): δ 157.6 (d, J = 249.8 Hz),
147.8 (t, J = 3.2 Hz), 142.3 (d, J = 11.3 Hz), 135.2 (d, J = 2.8 Hz,
3C), 133.9 (d, J = 10.2 Hz, 6C), 130.1 (d, J = 12.6 Hz, 6C), 129.5 (d,
J = 8.3 Hz), 125.2 (d, J = 2.3 Hz), 124.7 (d, J = 3.0 Hz), 117.9 (d, J =
86.0 Hz, 3C), 117.2 (dd, J = 12.0, 1.9 Hz), 116.2 (d, J = 21.0 Hz),
114.6 (d, J = 8.5 Hz), 111.3 (dd, J = 10.9, 2.9 Hz), 23.2 (d, J = 50.2
Hz). HRMS (ESI+) m/z: [M − Br]+ Calcd for C29H23FOP+
437.1465; found 437.1476.
[1-(2-Hydroxyphenyl)ethyl]triphenylphosphonium Bromide (2l).
1
Yield: 3.80 g, 82%; white solid, mp 158−160 °C; H NMR (400
MHz, DMSO-d6): δ 10.13 (s, 1H), 7.93−7.88 (m, 3H), 7.75−7.69
(m, 6H), 7.68−7.60 (m, 6H), 7.21−7.11 (m, 1H), 6.86 (d, J = 8.2 Hz,
1H), 6.61−6.59 (m, 1H), 6.51 (d, J = 8.2 Hz, 1H), 5.47 (dq, J = 14.5,
7.3 Hz, 1H), 1.73 (dd, J = 18.6, 7.3 Hz, 3H). 13C{1H} NMR (100
MHz, DMSO-d6): δ 155.3 (d, J = 6.1 Hz), 135.0 (d, J = 2.8 Hz, 3C),
134.2 (d, J = 9.3 Hz, 6C), 130.1 (d, J = 12.1 Hz, 6C), 129.2 (d, J = 4.8
Hz), 119.6 (d, J = 5.0 Hz), 119.4 (d, J = 2.4 Hz), 117.6 (d, J = 82.4
Hz, 3C), 115.8 (d, J = 2.0 Hz), 66.4, 28.1 (d, J = 45.6 Hz), 16.7.
HRMS (ESI+) m/z: [M − Br]+ Calcd for C26H24PO+ 383.1559;
found 383.1565.
[(5-Formylfuran-2-yl)methyl]triphenylphosphonium Bromide
(4f).33 Yield: 4.74 g, 83%; yellow solid, mp 261−263 °C; H NMR
1
(400 MHz, DMSO-d6): δ 9.43 (s, 1H), 7.99−7.87 (m, 3H), 7.82−
7.70 (m, 12H), 7.45 (d, J = 3.1 Hz, 1H), 6.48 (t, J = 3.1 Hz, 1H), 5.69
(d, J = 15.7 Hz, 2H). 13C{1H} NMR (100 MHz, DMSO-d6): δ 177.8,
152.7 (d, J = 1.5 Hz), 148.8 (d, J = 10.9 Hz), 135.3 (d, J = 1.2 Hz,
3C), 133.8 (d, J = 10.4 Hz, 6C), 130.2 (d, J = 12.7 Hz, 6C), 124.1 (d,
J = 2.7 Hz), 117.5 (d, J = 88.2 Hz, 3C), 114.9 (d, J = 7.8 Hz), 23.3 (d,
J = 50.8 Hz). HRMS (ESI+) m/z: [M − Br]+ Calcd for C24H20O2P+
371.1195; found 371.1202.
Triphenyl(prop-2-en-1-yl)phosphonium Bromide (2m).30 Yield:
1
2.95 g, 77%; white solid, mp 225−227 °C; H NMR (400 MHz,
DMSO-d6): δ 7.95−7.88 (m, 3H), 7.86−7.75 (m, 12H), 5.84−5.63
(m, 1H), 5.46−5.29 (m, 2H), 4.65 (dd, J = 16.7, 7.2 Hz, 2H). 13C
{1H} NMR (100 MHz, DMSO-d6): δ 135.0 (d, J = 2.9 Hz, 3C), 133.8
(d, J = 10.0 Hz, 6C), 130.2 (d, J = 12.5 Hz, 6C), 125.0 (d, J = 13.4
Hz), 124.5 (d, J = 9.7 Hz), 118.2 (d, J = 85.8 Hz, 3C), 26.5 (d, J =
49.5 Hz). HRMS (ESI+) m/z: [M − Br]+ Calcd for C21H20P+
303.1297; found 303.1298.
[1-(5-Methylfuran-2-yl)ethyl]triphenylphosphonium Bromide
1
(4g). Yield: 3.78 g, 84%; beige solid, mp 172−173 °C; H NMR
(400 MHz, DMSO-d6): δ 7.93−7.87 (m, 3H), 7.83−7.72 (m, 12H),
6.15 (t, J = 3.6 Hz, 1H), 6.01 (d, J = 3.0 Hz, 1H), 5.97 (dq, J = 14.2,
7.2 Hz, 1H), 2.02 (d, J = 2.0 Hz, 3H), 1.61 (dd, J = 18.2, 7.2 Hz, 3H).
13C{1H} NMR (100 MHz, DMSO-d6): δ 152.7 (d, J = 3.8 Hz), 144.3
(Furan-2-ylmethyl)triphenylphosphonium Bromide (4a).31 Yield:
1
3.55 g, 84%; beige solid, mp 274−276 °C; H NMR (400 MHz,
(d, J = 8.8 Hz), 135.0 (d, J = 2.9 Hz, 3C), 134.1 (d, J = 9.5 Hz, 6C),
130.1 (d, J = 12.2 Hz. 6C), 117.4 (d, J = 82.9 Hz, 3C), 112.4 (d, J =
7.9 Hz), 107.2 (d, J = 2.9 Hz), 28.9 (d, J = 46.7 Hz), 14.1−13.0 (d, J
= 1.2 Hz). HRMS (ESI+) m/z: [M − Br]+ Calcd for C25H24OP+
371.1559; found 371.1545.
DMSO-d6): δ 7.93−7.89 (m, 3H), 7.82−7.65 (m, 12H), 7.59 (br s,
1H), 6.41 (br s, 1H), 6.16 (t, J = 3.2 Hz, 1H), 5.47 (d, J = 14.8 Hz,
2H). 13C{1H} NMR (100 MHz, DMSO-d6): δ 144.1 (d, J = 4.3 Hz),
141.8 (d, J = 11.0 Hz), 135.2 (d, J = 3.5 Hz, 3C), 133.8 (d, J = 10.5
Hz, 6C), 130.1 (d, J = 12.8 Hz, 6C), 117.9 (d, J = 86.1 Hz, 3C), 112.1
(d, J = 8.4 Hz), 111.4 (d, J = 3.8 Hz), 22.8 (d, J = 50.9 Hz). HRMS
(ESI+) m/z: [M − Br]+ Calcd for C23H20OP+ 343.1246; found
343.1248.
[1-(5-Methylfuran-2-yl)(phenyl)methyl]triphenylphosphonium
Bromide (4h).34 Yield: 4.25 g, 83%; beige solid, mp 210−212 °C; 1H
1
NMR (400 MHz, DMSO-d6): δ H NMR (400 MHz, DMSO-d6) δ
7.96−7.86 (m, 3H), 7.79−7.66 (m, 6H), 7.60−7.47 (m, 6H), 7.44−
7.37 (m, 1H), 7.36−7.30 (m, 2H), 7.28−7.15 (m, 3H), 6.26 (t, J =
3.2 Hz, 1H), 6.10 (br s, 1H), 2.10 (s, 3H).13C{1H} NMR (100 MHz,
DMSO-d6): δ 153.3 (d, J = 3.3 Hz), 143.2 (d, J = 7.9 Hz), 135.3 (d, J
= 2.8 Hz, 3C), 134.5 (d, J = 9.4 Hz, 6C), 130.6(d, J = 6.0 Hz, 2C),
130.5, 130.0 (d, J = 12.3 Hz, 6C), 129.4(d, J = 2.8 Hz), 129.1 (d, J =
1.6 Hz, 2C), 117.1 (d, J = 82.6 Hz, 3C), 113.5 (d, J = 7.8 Hz), 107.5,
41.3 (d, J = 44.3 Hz), 13.1. HRMS (ESI+) m/z: [M − Br]+ Calcd for
C30H26OP+ 433.1716; found 433.1730.
[(5-Methylfuran-2-yl)methyl]triphenylphosphonium Bromide
(4b).32 Yield: 3.80 g, 87%; beige solid, mp 215−217 °C; H NMR
1
(400 MHz, DMSO-d6): δ 7.97−7.93 (m, 3H), 7.82−7.64 (m, 12H),
6.05 (t, J = 3.4 Hz, 1H), 6.00 (br s, 1H), 5.38 (d, J = 14.5 Hz, 2H),
2.04 (s, 3H). 13C{1H} NMR (100 MHz, DMSO-d6): δ 152.6 (d, J =
4.0 Hz), 139.6 (d, J = 11.3 Hz), 135.1 (d, J = 2.8 Hz, 3C), 133.8 (d, J
= 10.1 Hz, 6C), 130.1 (d, J = 12.5 Hz, 6C), 118.0 (d, J = 85.8 Hz,
3C), 112.9 (d, J = 8.3 Hz), 107.3 (d, J = 3.2 Hz), 23.0 (d, J = 50.4
Hz), 13.0. HRMS (ESI+) m/z: [M − Br]+ Calcd for C24H22OP+
357.1403; found 357.1396.
(1H-Indol-3-ylmethyl)triphenylphosphonium Bromide (4i). Yield:
1
3.72 g, 79%; beige solid, mp 263−265 °C; H NMR (400 MHz,
{[5-(4-Nitrophenyl)furan-2-yl]methyl}]triphenylphosphonium
1
Bromide (4c). Yield: 4.56 g, 85%; yellow solid, mp 286−288 °C; H
DMSO-d6): δ 11.24 (s, 1H), 7.85 (t, J = 7.0 Hz, 3H), 7.78−7.63 (m,
12H), 7.33 (d, J = 8.0 Hz, 1H), 7.16 (d, J = 8.0 Hz, 1H), 7.02 (t, J =
7.4 Hz, 1H), 6.84 (t, J = 7.4 Hz, 1H), 6.77 (t, J = 7.4 Hz, 1H), 5.28
(d, J = 13.7 Hz, 3H). 13C{1H} NMR (100 MHz, DMSO-d6): δ 135.4,
134.8 (d, J = 2.8 Hz, 3C), 134.0 (d, J = 9.7 Hz, 6C), 131.5 (d, J = 9.8
Hz), 130.0 (d, J = 12.2 Hz, 6C), 128.8 (d, J = 11.6 Hz), 121.6, 118.9,
118.6 (d, J= 84.7 Hz, 3C), 118.4, 111.6, 99.2 (d, J = 8.6 Hz), 20.0 (d,
J = 48.6 Hz). HRMS (ESI+) m/z: [M − Br]+ Calcd for C27H23PN+
392.1563; found 392.1568.
NMR (400 MHz, DMSO-d6): δ 8.20 (d, J = 8.8 Hz, 2H), 8.01−7.88
(m, 3H), 7.84−7.72 (m, 12H), 7.47 (d, J = 8.8 Hz, 2H), 7.27 (d, J =
2.9 Hz, 1H), 6.53 (t, J = 3.4 Hz, 1H), 5.64 (d, J = 15.1 Hz, 2H).
13C{1H} NMR (100 MHz, DMSO-d6): δ 151.7 (d, J = 3.9 Hz), 146.1,
144.4 (d, J = 12.1 Hz), 135.3 (d, J = 2.7 Hz, 3C), 135.0 (d, J = 2.0
Hz), 133.9 (d, J = 10.2 Hz, 6C), 130.2 (d, J = 12.6 Hz, 6C), 124.4
(2C), 124.7 (2C), 117.9 (d, J = 86.0 Hz, 3C), 115.2 (d, J = 8.3 Hz),
111.4 (d, J = 3.1 Hz), 23.5 (d, J = 50.5 Hz). HRMS (ESI+) m/z: [M
− Br]+ Calcd for C29H23NO3P+ 464.1410; found 464.1428.
[(1-Benzyl-1H-pyrazol-4-yl)methyl]triphenylphosphonium Bro-
mide (4j). Yield: 4.40 g, 86%; white solid, mp 236−237 °C; 1H
NMR (400 MHz, DMSO-d6): δ 7.93−7.84 (m, 3H), 7.77−7.62 (m,
12H), 7.38 (d, J = 2.2 Hz, 1H), 7.36−7.20 (m, 3H), 7.06 (d, J = 6.6
Hz, 2H), 7.00 (s, 1H), 5.24 (s, 2H), 5.09 (d, J = 14.0 Hz, 2H).
13C{1H} NMR (100 MHz, DMSO-d6): δ 139.8 (d, J = 4.2 Hz), 137.1,
({5-[4-(Trifluoromethyl)phenyl]furan-2-yl}methyl)triphenylphos-
phonium Bromide (4d).29 Yield: 4.70 g, 83%; white solid, mp 258−
1
260 °C; H NMR (400 MHz, DMSO-d6): δ 7.98−7.91 (m, 3H),
7.83−7.73 (m, 12H), 7.70 (d, J = 8.3 Hz, 2H), 7.43 (d, J = 8.3 Hz,
2H), 7.14 (d, J = 3.0 Hz, 1H), 6.49 (t, J = 3.4 Hz, 1H), 5.61 (d, J =
15.0 Hz, 2H).13C{1H} NMR (100 MHz, DMSO-d6): δ 152.1 (d, J =
3.6 Hz), 143.2 (d, J = 12.0 Hz), 135.2 (d, J = 2.7 Hz, 3C), 133.9 (d, J
= 10.2 Hz, 6C), 132.9, 130.2 (d, J = 12.6 Hz, 6C), 127.6 (q, J = 31.8
Hz), 125.8 (q, J = 3.6 Hz, 2C), 124.1 (q, J = 271.8 Hz, 2C), 123.6,
118.0 (d, J = 86.0 Hz, 3C), 114.7 (d, J = 8.3 Hz), 109.6 (d, J = 3.0
Hz), 23.4 (d, J = 50.4 Hz). HRMS (ESI+) m/z: [M − Br]+ Calcd for
C30H23F3OP+ 487.1433; found 487.1451.
135.0 (d, J = 2.7 Hz, 3C), 133.8 (d, J = 9.8 Hz, 6C), 131.1 (d, J = 5.5
Hz), 130.1 (d, J = 12.4 Hz, 6C), 128.5, 127.7, 127.4 (2C), 118.1 (d, J
= 85.4 Hz, 3C), 106.3 (d, J = 7.6 Hz), 54.7, 18.7 (d, J = 50.3 Hz).
+
HRMS (ESI+) m/z: [M − Br]+ Calcd for C29H26PN2 433.1828;
found 433.1835.
(1-Thiophen-2-ylethyl)triphenylphosphonium Bromide (4k).35
1
Yield: 3.71 g, 82%; white solid, mp 165−167 °C; H NMR (400
9842
J. Org. Chem. 2021, 86, 9838−9846