B. A. Trofimov et al. / Tetrahedron Letters 45 (2004) 9143–9145
9145
26
Compound 3a: colorless oil, ½aꢀD ꢁ15.6 (c 1.5, EtOH). 1H
Elemental analysis: Calcd for C22H41O7P (448.53): C,
58.91; H, 9.21; P, 6.91%. Found: C, 58.76; H, 9.43; P,
6.78%.
NMR (400.13MHz, CDCl3): d 0.90 (t, 6H, 3J = 6.4Hz,
Me, 1.30 (s, 3H, Me), 1.35 (s, 3H, Me), 1.38 (m, 10H,
CH2CH2CH2P), 1.43 (s, 3H, Me), 1.48 (m, 5H, C-10, Me),
1.66–1.70 (m, 2H, CH2P), 3.68–3.72 (m, 2H, H-9), 3.86 (d,
26
1
Compound 4b: colorless oil, ½aꢀD ꢁ1.9 (c 4.0, CCl4); H
NMR (400.13MHz, CDCl3): d 1.25 (s, 3H, Me), 1.29 (s,
3H, Me), 1.38 (s, 3H, Me), 1.48 (s, 3H, Me), 2.0–2.12 (m,
6H, H-10, CH2P), 2.80–2.98 (m, 4H, CH2Ph), 3.80–3.85
(m, 2H, H-9), 3.96–4.15 (m, 4H, H-3,4,6), 4.17–4.21 (m,
1H, H-5), 4.61 (d, 1H, 3J1,2 = 3.2Hz, H-2), 5.78 (d, 1H, H-
1), 7.16–7.28 (m, 10H, Ph). 13C NMR (100.69MHz): d
25.44, 26.23, 26.83, 26.98 (4Me), 27.81 (d, 2JP,C = 18.4Hz,
1H, J3,4 = 3.0Hz, H-3), 3.96 (dd, 1H, 2J = 8.3Hz,
3
3J5,6 = 5.5Hz, H-6), 4.06 (dd, 1H, 2J = 8.3Hz,
3J5,6 = 5.8Hz, H-6), 4.09 (dd, 1H, 3J4,5 = 6.8Hz,
3J3,4 = 3.0Hz, H-4), 4.12–4.16 (m, 1H, H-5), 4.51 (d, 1H,
3J1,2 = 3.1Hz, H-2), 5.92 (d, 1H, H-1). 13C NMR
3
(100.69MHz): d 13.85 (Me), 24.50 (d, JP,C = 10.7Hz,
CH2Me), 25.23, 25.50, 26.24 (3Me), 26.56 (d,
2
CH2Ph), 27.83 (d, JP,C = 17.7Hz, CH2Ph), 28.89 (d,
1JP,C = 12.0Hz, C-10), 26.90 (Me), 27.10 (d,
1JP,C = 63.0Hz, C-10), 30.82 (d, JP,C = 62.5Hz, CH2P),
1
2JP,C = 11.1Hz, CH2CH2P), 27.17 (d, JP,C = 11.5Hz,
CH2CH2P), 27.98 (d, JP,C = 14.4Hz, CH2P), 28.02 (d,
31.35 (d, JP,C = 62.5Hz, CH2P), 63.92 (d, JP,C = 2.8Hz,
C-9), 67.55 (C-6), 72.35 (C-5), 81.02 (C-4), 82.22
(C-3), 82.52 (C-2), 105.26 (C-1), 109.29 and 111.92
(C-7,8), 126.08 (C-p), 128.06 and 128.12 (C-o), 128.83
2
1
2
1
1JP,C = 14.6Hz, CH2P), 67.62 (C-6), 68.91 (d, JP,C
=
2
21.0Hz, C-9), 72.57 (C-5), 81.21 (C-3), 82.27 (C-4), 85.19
(C-2), 105.34 (C-1), 109.54 and 111.80 (C-7,8). 31P NMR
(161.98MHz): d ꢁ33.94. Elemental analysis: Calcd for
C22H41O6P (432.53): C, 61.09; H, 9.55; P, 7.16%. Found:
C, 61.05; H, 9.67; P, 7.39%.
3
(C-m), 140.91 (d, JP,C = 13.7Hz, C-i). 31P NMR (161.98
MHz): d 46.18. Elemental analysis: Calcd for C30H41O7P
(544.62): C, 66.16; H, 7.59; P, 5.69%. Found: C, 66.22; H,
7.32; P, 5.85%.
26
1
Compound 3b: colorless oil, ½aꢀ ꢁ7.1 (c 1.0, EtOH); H
NMR (400.13MHz, CDCl3): dD1.31 (s, 6H, Me), 1.43 (s,
3H, Me), 1.53 (s, 3H, Me), 1.73–1.81(m, 6H, H-10, CH2P),
2.71–2.86 (m, 4H, CH2Ph), 3.64–3.77 (m, 2H, H-9), 3.84
15. General procedure for the preparation of 5: A mixture of
phosphine 3 and elemental sulfur in toluene was heated at
50°C upon stirring under argon for 3h. The crude
product, a viscous undistillable liquid, was purified by
column chromatography on Al2O3 (hexane) to give the
phosphine sulfide 5 (Table 2).
3
(d, 1H, J3,4 = 2.7Hz, H-3), 3.99 (dd, 1H, 2J = 8.8Hz,
3
3J5,6 = 5.9Hz, H-6), 4.06 (dd, 1H, 2J = 8.8Hz, J5,6
=
26
3
3
5.9Hz, H-6), 4.09 (dd, 1H, J4,5 = 7.7Hz, J3,4 = 2.7Hz,
H-4), 4.34 (dd, 1H, 3J4,5 = 7.7Hz, 3J5,6 = 5.9Hz, H-5), 4.53
(d, 1H, J1,2 = 3.7Hz, H-2), 5.83 (d, 1H, H-1), 7.17–7.30
Compound 5a: yellow solid, mp 98–99°C (hexane), ½aꢀD
ꢁ7.1 (c 1.0, EtOH); 1H NMR (400.13MHz, CDCl3): d
0.90–0.95 (m, 6H, Me), 1.25 (s, 3H, Me), 1.31 (s, 3H, Me),
1.34 (s, 3H, Me), 1.41 (m, 4H, CH2Me), 1.48 (s, 3H, Me),
1.54–1.58 (m, 4H, CH2CH2P), 1.81–1.86 (m, 6H, H-10,
3
(m, 10H, Ph). 13C NMR (100.69MHz): d 23.44, 25.17,
1
25.23, 25.48 (4Me), 27.67 (d, JP,C = 14.9Hz, C-10), 29.38
1
(d, JP,C = 13.2, CH2P) 29.47 (d, JP,C = 13.6Hz, CH2P),
1
2
CH2P), 3.80–3.91 (m, 2H, H-9), 3.98 (dd, 1H, J = 8.5Hz,
2
32.23 (d, JP,C = 14.2Hz, CH2Ph), 67.55 (C-6), 68.66 (d,
3J5,6 = 5.5Hz, H-6), 4.03–4.07 (m, 2H, H-3,6), 4.08–4.14
(m, 1H, H-4), 4.18–4.25 (m, 1H, H-5), 4.72 (d, 1H,
3J1,2 = 3.3Hz, H-2), 5.82 (d, 1H, H-1). 13C NMR
(100.69MHz): d = 13.58 (Me), 23.78 (CH2Me), 24.03
2JP,C = 19.7Hz, C-9), 72.47 (C-5), 81.18 (C-4), 82.18 (C-3),
82.75 (C-2), 105.26 (C-1), 109.02 and 111.80 (C-7,8),
126.08 (C-p), 128.13 (C-o), 128.52 (C-m), 142.69 (d,
3JP,C = 10.4Hz, C-i), 142.73 (d, JP,C = 10.3Hz, C-i). 31P
(CH2Me), 24.50 (d, JP,C = 16.2Hz, CH2CH2P), 24.57 (d,
2JP,C = 16.2Hz, CH21CH2P), 25.42, 26.14, 26.72, 26.83
(4Me), 30.48 (d, JP,C = 49.9Hz, C-10), 31.30 (d,
3
2
NMR (161.98MHz): d ꢁ31.18. Elemental analysis: Calcd
for C30H41O6P (528.62): C, 68.17; H, 7.82; P, 5.86%.
Found: C, 68.39; H, 7.73; P, 5.65%.
1
1JP,C = 51.4Hz, CH2P), 32.38 (d, JP,C = 50.4Hz, CH2P),
64.26 (d, JP,C = 2.9Hz, C-9), 67.35 (C-6), 72.26 (C-5),
2
14. General procedure for the preparation of 4: A solution of
phosphine 3 in hexane was stirred at rt under air or O2
atmosphere. After reaction completion, as indicated by
TLC, the solvent was removed under reduced pressure to
afford phosphine oxide 4 (Table 2).
80.79 (C-4), 81.90 (C-3), 82.09 (C-2), 105.17 (C-1), 109.06
and 111.74 (C-7,8). 31P NMR (161.98MHz): d 46.73.
Elemental analysis: Calcd for C22H41O6PS (464.60): C,
56.88; H, 8.89; P, 6.67; S, 6.90%. Found: C, 56.98; H, 8.69;
P, 6.51; S, 6.72%.
26
1
Compound 4a: colorless oil, ½aꢀ ꢁ12.2 (c 0.5, CCl4); H
NMR (400.13MHz, CDCl3): dD0.89 (t, 6H, 3J = 7.2Hz,
Me, 1.21–1.31 (m, 4H, CH2Me), 1.28 (s, 3H, Me), 1.32–
1.39 (m, 2H, CH2CH2P), 1.33 (s, 3H, Me), 1.41 (s, 3H,
Me), 1.46 (s, 3H, Me), 1.47–1.58 (m, 3H, CH2CH2P),
1.63–1.71 (m, 2H, CH2P), 1.94–2.00 (m, 1H, CH2P), 2.22–
2.28 (m, 2H, H-10), 3.79–3.85 (m, 2H, H-9), 3.95 (dd, 1H,
26
Compound 5b: yellow solid, mp 87–88°C (hexane), ½aꢀD
ꢁ25.7 (c 1.0, CCl4). 1H NMR (400.13MHz, CDCl3): d
1.26 (s, 3H, Me), 1.29 (s, 3H, Me), 1.38 (s, 3H, Me), 1.47
(s, 3H, Me), 1.96–2.17 (m, 6H, H-10, CH2P), 2.89–2.94 (m,
4H, CH2Ph), 3.82–3.90 (m, 2H, H-9), 3.94–4.02 (m, 3H,
H-3,6), 4.05–4.12 (m, 1H, H-4), 4.14–4.20 (m, 1H, H-5),
3
3
2J = 8.6Hz, J5,6 = 5.3Hz, H-6), 4.03 (m, 1H, H-3), 4.12
4.73 (d, 1H, J1,2 = 3.3Hz, H-2), 5.78 (d, 1H, H-1), 7.16–
7.28 (m, 10H, Ph).13C NMR (100.69MHz): d 25.11, 26.14,
26.71, 26.86 (4Me), 28.60 (d, JP,C = 27.0Hz, CH2Ph),
3
(dd, 1H, 2J = 8.6Hz, J5,6 = 6.3Hz, H-6), 4.28–4.33 (m,
3
2
2H, H-4,5), 4.49 (d, 1H, J1,2 = 3.6Hz, H-2), 5.90 (d, 1H,
H-1). 13C NMR (100.69MHz): d 13.54 (Me), 23.56 (d,
3JP,C = 3.8Hz, CH2Me), 23.78 (d, 3JP,C = 3.8Hz, CH2Me),
24.15 (d, 2JP,C = 13.9Hz, CH2CH2P), 24.17 (d,
2JP,C = 14.8Hz, CH21CH2P), 25.07, 26.10, 26.68, 26.77
(4Me), 28.28 (d, JP,C = 66.1Hz, C-10), 28.34 (d,
1
1
30.90 (d, JP,C = 49.7Hz, C-10), 33.31 (d, JP,C = 48.4Hz,
1
CH2P), 34.19 (d, JP,C = 47.5Hz, CH2P), 64.23 (d,
2JP,C = 3.6Hz, C-9), 67.41 (C-6), 72.18 (C-5), 80.88 (C-
4), 81.93 (C-3), 82.20 (C-2), 105.14 (C-1), 109.15 and
111.80 (C-7,8), 126.51 and 126.54 (C-p), 128.06 and 128.18
1
3
1JP,C = 63.9Hz, CH2P), 28.80 (d, JP,C = 65.4Hz, CH2P),
(C-o), 128.68 (C-m), 140.52 (d, JP,C = 14.6Hz, C-i). 31P
2
63.78 (d, JP,C = 3.2Hz, C-9), 67.53 (C-6), 73.35 (C-5),
NMR (161.98MHz): d 48.03. Elemental analysis: Calcd
for C30H41O6PS (560.69): C, 64.27; H, 7.37; P, 5.52; S,
5.72%. Found: C, 64.45; H, 7.55; P, 5.35; S, 5.58%.
75.02 (C-4), 81.06 (C-3), 85.02 (C-2), 105.19 (C-1), 109.52
and 111.72 (C-7,8). 31P NMR (161.98MHz): d 48.39.