2008
L. Wang et al.
LETTER
(9) General Procedure for 5: CBr4 was added to the solution of
7-phosphanorbornenes in toluene and heated at 90–120 °C
for 10 min to 4 h. The reactions were monitored by 31P NMR
J
J
H–H = 7.8 Hz, 1 H), 7.92 (d, JH–H = 8.4 Hz, 1 H), 9.00 (d,
H–H = 8.4 Hz, 1 H). 13C NMR (CDCl3): δ = 14.15 (d, 3JC–P
=
2.4 Hz, Me), 40.64 (d, 2JC–P = 4.8 Hz, CH2), 124.31 (d, JC–P
= 14.8 Hz), 126.21 (s), 126.44 (s), 127.77 (d, 4JC–P = 5.4 Hz),
128.67 (d, 4JC–P = 1.7 Hz), 130.35 (d, 3JC–P = 9.4 Hz), 131.30
(d, JC–P = 124.6 Hz, P–C), 132.35 (d, 3JC–P = 3.4 Hz), 132.70
(d, 2JC–P = 10.9 Hz), 134.39 (d, 3JC–P = 10.4 Hz). 31P NMR
(CDCl3): δ = 73.4. HRMS (ESI): m/z [M + Na]+ calcd for
C18H27N2PSNa: 357.1530; found: 357.1528. Anal. Calcd for
C18H27N2PS: C, 64.64; H, 8.14; N, 8.38. Found: C, 64.61; H,
8.37; N, 7.79. 5e: 1H NMR (CDCl3): δ = 1.00 (t, JH–H = 7.2
Hz, 12 H, Me), 2.96–3.18 (m, 8 H, Et), 3.41 (d, JH–P = 14.7
Hz, 2 H, P–CH2), 7.21–7.31 (m, 3 H), 7.40–7.43 (m, 2 H).
13C NMR (CDCl3): δ = 13.93 (d, 3JC–P = 3.6 Hz, Me), 39.61
(d, 2JC–P = 3.4 Hz, CH2), 39.66 (d, JC–P = 84.7 Hz, P–CH2),
126.82 (d, 5JC–P = 3.7 Hz, p-Ph), 127.92 (d, 4JC–P = 3.2 Hz, 2
× C, m-Ph), 130.67 (d, 3JC–P = 5.7 Hz, 2 × C, o-Ph), 132.49
(d, 2JC–P = 6.1 Hz). 31P NMR (CDCl3): δ = 81.9. HRMS
(ESI): m/z [M + Na]+ calcd for C15H27N2PSNa: 321.1530;
found: 321.1526.
spectroscopy. 4a: 31P NMR (toluene): δ = 150.6, 4b: 31
P
NMR (toluene): δ = 152.1, 4c: 31P NMR (toluene): δ = 129.0,
4d: 31P NMR (toluene): δ = 151.1, 4e: 31P NMR (toluene):
δ = 172.4. The solution was cooled to 0 °C, and Et2NH was
added. After the mixture was warmed to r.t. and stirred for
30 min, S8 was added and reacted for 1 h. The mixture was
filtered through silica to remove salts and concentrated.
Purification was performed via column chromatography on
silica gel. 5a: 1H NMR (CDCl3): δ = 1.04 (t, JH–H = 7.1 Hz,
12 H, Me), 3.07–3.20 (m, 8 H, CH2), 7.38–7.45 (m, 3 H),
7.92–8.00 (m, 2 H). 13C NMR (CDCl3): δ = 13.31 (d, 3JC–P
4.0 Hz, Me), 39.19 (d, 2JC–P = 4.2 Hz, CH2), 128.01 (d, 2JC–P
=
=
13.2 Hz, o-Ph), 130.81 (d, 4JC–P = 2.9 Hz, p-Ph), 131.44 (d,
3JC–P = 10.6 Hz, m-Ph), 135.45 (d, JC–P = 124.3 Hz, P–C). 31
P
NMR (CDCl3): δ = 77.6. HRMS (ESI): m/z [M + Na]+ calcd
for C14H25N2PSNa: 307.1374; found: 307.1375. 5b: 1H
NMR (CDCl3): δ = 1.04 (t, JH–H = 7.2 Hz, 12 H, Me), 3.07–
3.19 (m, 8 H, CH2), 3.84 (s, 3 H, OMe), 6.93 (dd, 4JH–P = 2.7
Hz, JH–H = 9.0 Hz, 2 H, m-Ph), 7.88 (dd, 3JH–P = 12.6 Hz,
JH–H = 9.0 Hz, 2 H, o-Ph). 13C NMR (CDCl3): δ = 13.37 (d,
3JC–P = 4.1 Hz, Me), 39.20 (d, 2JC–P = 4.3 Hz, CH2), 55.28 (s,
(10) 4f: 1H NMR (CDCl3): δ = 7.13–7.69 (m, 7 H), 8.36 (ddd,
J = 1.5, 3.3, 7.8 Hz, 1 H). 13C NMR (CDCl3): δ = 124.23 (d,
4JC–P = 5.0 Hz, C–Br), 127.43 (s), 129.32 (d, JC–P = 3.2 Hz),
129.53 (s), 130.25 (s), 131.65 (d, JC–P = 5.0 Hz), 132.29 (s),
132.75 (s), 133.74 (d, JC–P = 1.5 Hz), 137.50 (d, JC–P = 62.1
Hz, P–C), 139.41 (d, 3JC–P = 8.3 Hz), 143.15 (d, 2JC–P = 43.9
Hz). 31P NMR (CDCl3): δ = 150.2.
OMe), 113.41 (d, 2JC–P = 14.4 Hz, o-Ph), 126.68 (d, JC–P
=
130.4 Hz, P–C), 133.39 (d, 3JC–P = 12.0 Hz, m-Ph), 161.70
(d, 4JC–P = 3.2 Hz, p-Ph). 31P NMR (CDCl3): δ = 77.0. HRMS
(ESI): m/z [M + Na]+ calcd for C15H27N2OPSNa: 337.1479;
found: 337.1483. Anal. Calcd for C15H27N2OPS: C, 57.30;
H, 8.66; N, 8.91. Found: C, 58.12; H, 8.65; N, 8.01. 5c: 1H
NMR (CDCl3): δ = 1.09 (t, JH–H = 7.1 Hz, 12 H, Me), 3.14–
3.25 (m, 8 H, CH2), 7.01 (dd, JH–P = 5.1 Hz, JH–H = 3.6 Hz,
1 H, Th-CH), 7.15 (dd, JH–P = 2.7 Hz, JH–H = 3.8 Hz, 1 H,
Th-CH), 7.24 (m, 2 H, Th-CH), 7.46 (dd, JH–P = 8.0 Hz,
JH–H = 3.6 Hz, 1 H, Th-CH). 13C NMR (CDCl3): δ = 13.34
(d, 3JC–P = 4.2 Hz, Me), 39.14 (d, 2JC–P = 4.5 Hz, CH2),
124.07 (d, 2JC–P = 14.2 Hz, Th-CH), 124.60 (s, Th-CH),
125.42 (s, Th-CH), 128.01 (s, Th-CH), 135.34 (d, 3JC–P = 9.4
Hz, Th-CH), 136.45 (s, Th-CH), 137.18 (d, JC–P = 134.0 Hz,
P–C), 144.21 (d, 4JC–P = 6.0 Hz, Th-C). 31P NMR (CDCl3): δ
= 65.8. HRMS (ESI): m/z [M + Na]+ calcd for
(11) Vincent, E.; Verdonck, L.; Van der Kelen, G. P. J. Mol.
Struct. 1980, 65, 239.
(12) Nelson, J. H. Nuclear Magnetic Resonance Spectroscopy;
Pearson Education: Upper Saddle River, N.J., 2003, 172.
(13) 5f: 1H NMR (CDCl3): δ = 0.96 (t, JH–H = 7.2 Hz, 6 H, Me),
1.09 (t, JH–H = 7.2 Hz, 6 H, Me), 2.78–3.09 (m, 6 H, CH2),
3.21–3.31 (m, 2 H, CH2), 7.16–7.30 (m, 4 H), 7.40–7.50 (m,
2 H), 7.58–7.60 (m, 1 H), 7.90 (dd, J = 12.4, 7.6 Hz, 1 H).
13C NMR (CDCl3): δ = 13.6 (d, 3JC–P = 5.2 Hz, Me), 13.7 (d,
3JC–P = 2.0 Hz, Me), 39.7 (d, 2JC–P = 4.5 Hz, CH2), 39.9 (d
2JC–P = 3.8 Hz, CH2), 124.4 (s, C–Br), 126.0 (s), 127.1 (d,
J
C–P = 11.5 Hz), 128.7 (s), 130.0 (d, JC–P = 2.8 Hz), 131.4 (s),
131.6 (d, JC–P = 7.2 Hz), 132.2 (s), 133.0 (d, JC–P = 125.5 Hz,
P–C), 133.4 (d, JC–P = 11.9 Hz), 142.3 (d, 3JC–P = 3.9 Hz),
144.9 (d, 2JC–P = 11.8 Hz). 31P NMR (CDCl3): δ = 73.1.
HRMS (ESI): m/z [M + Na]+ calcd for C20H28N2PSBrNa:
461.0792; found: 461.0792. Anal. Calcd for C20H28N2PSBr:
C, 54.67; H, 6.42. Found: C, 55.45; H, 6.34.
C16H25N2PS3Na: 395.0815; found: 395.0817. Anal. Calcd
for C16H25N2PS3: C, 51.58; H, 6.76; N, 7.52. Found: C,
51.11; H, 6.71; N, 6.57. 5d: 1H NMR (CDCl3): δ = 1.16 (t,
J
H–H = 7.1 Hz, 12 H, Me), 3.15–3.41 (m, 8 H, CH2), 7.41–
7.60 (m, 3 H), 7.70 (ddd, J = 1.2, 7.2, 16.5 Hz, 1 H), 7.84 (d,
Synlett 2013, 24, 2006–2008
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