usual. The product (642 mg) was chromatographed over a SiO (24 g) column with gradient elution bypetroleum ether:AcOEt
2
to afford 8-phenylsulfonylgeranylfarnesol (2, 344 mg, 50%) as a colorless oil, C H SO .
31 46
3
IR spectrum (liquid film, ν, cm −1): 3458, 2922, 1446, 1304, 1145, 1084, 990.
PMR spectrum (300 MHz, δ , ppm, J/Hz): 1.54 (3H, s, H -23), 1.55 (3H, s, H -22), 1.58 (3H, s, H -21), 1.61 (3H, s,
H
3
3
3
H -20), 1.65 (3H, s, H -25), 1.68 (3H, s, H -24), 3.46 (1H, dd, J = 4.0, J = 11.7, H-8), 4.11 (2H, d, J = 6.7, H -1), 4.86 (1H,
3
3
3
1
2
2
t, J = 6.5, H-18), 5.04 (1H, t, J = 6.7, H-14), 5.14 (1H, t, J = 6.9, H-10), 5.23 (1H, t, J = 6.7, H-2), 5.35 (1H, t, J = 7.5, H-6),
7.50-7.88 (5H, m, Ar–H).
13
C NMRspectrum (75.5 MHz, δ , ppm): 16.4 (q, C-24), 16.5 (q, C-25), 16.6 (q, C-23), 16.7 (q, C-22), 18.1 (q, C-21),
C
24.8 (q, C-20), 26.6 (t, C-5), 26.1 (t, C-9), 26.9 (t, C-17), 27.1 (t, C-13), 39.1 (t, C-16), 40.0 (t, C-12), 40.1 (t, C-4), 59.6 (t,
C-1), 74.3 (t, C-8), 118.7 (d, C-10), 124.1 (d, C-14), 124.2 (d, C-2), 124.5 (d, C-18), 124.7 (d, C-6), 129.2 (d, C-3′), 129.3 (d,
C-2′), 131.7 (s, C-19), 133.9 (s, C-4′), 135.6 (s, C-15), 135.7 (s, C-11), 138.8 (s, C-3), 138.9 (s, C-7), 139.2 (s, C-1′).
+
Mass spectrum (m/z, I, %): 499 (3) [M + H] , 480 (5), 408 (4), 367 (5), 355 (7), 339 (56), 310 (7), 271 (23), 189 (22),
135 (72), 109 (100).
Synthesis of 8-Phenylsulfonylgeranylfarnesol Tetrahydropyranyl Ether (1). A solution of 2 (190 mg, 0.38 mmol)
in CH Cl (0.8 mL) was treated with dihydropyran (51 mg, 45.65 mmol) and pyridinium p-toluenesulfonate (PyTs 45 mg,
2
2
0.18 mmol) and stirred for 12 h at room temperature. The usual work up afforded crude product (236 mg) that was
chromatographed over a SiO (4 g) column with gradient elution bypetroleum ether:AcOEt toafford geranylfarnesol THP ether
2
(1, 200 mg, 90%) as a colorless liquid, C H SO .
36 54
4
IR spectrum (liquid film, ν, cm −1): 2924, 1446, 1383, 1305, 1146, 1083, 1023, 905, 813.
PMR spectrum (300 MHz, δ , ppm, J/Hz): 1.52 (3H, s, H -23), 1.55 (3H, s, H -22), 1.57 (3H, s, H -21), 1.59 (3H, s,
H
3
3
3
H -20), 1.60 (3H, s, H -25), 1.66 (3H, s, H -24), 3.48 (1H, dd, J = 8.4, J = 11.8, H-8), 3.96 (2H, dd, J = 7.6, J = 11.2, H -1),
3
3
3
1
2
1
2
2
4.16-4.23 (2H, m, H -5′′), 4.59 (1H, s, H-1′′), 4.87 (1H, t, J = 6.8, H-18), 5.06 (1H, t, J = 6.8, H-14), 5.19 (1H, t, J = 6.8, H-10),
2
5.25 (1H, t, J = 6.8, H-2), 5.37 (1H, t, J = 6.5, H-6), 7.47-7.87 (5H, m, Ar–H).
13
C NMR spectrum (75.5 MHz, δ , ppm): 16.4 (q, C-22 and C-23), 16.7 (q, C-25), 18.1 (q, C-21), 20.0 (t, C-9), 23.7
C
(t, C-4′′), 24.3 (q, C-24), 25.9 (q, C-20), 26.1 (t, C-3′′), 26.8 (t, C-13), 26.9 (t, C-17), 27.1 (t, C-5), 31.1 (t, C-12), 31.2 (t,
C-2′′), 40.0 (t, C-4), 40.1 (t, C-16), 62.7 (d, C-8), 62.8 (t, C-1), 64.1 (t, C-5′′), 98.4 (d, C-1′′), 118.8 (d, C-10), 121.3 (d, C-2),
121.5 (d, C-14), 124.2 (d, C-18), 124.7 (d, C-6), 126.7 (s, C-19), 129.1 (s, C-7), 129.3 (d, C-2′), 131.7 (d, C-3 ), 133.9 (s, C-2),
135.6 (s, C-4′), 135.8 (s, C-11), 138.8 (s, C-15), 139.2 (s, C-1′).
+
Mass spectrum (m/z, I, %): 498 (3) [M - C H O] , 480 (21), 422 (6), 355 (5), 339 (100), 271 (21), 203 (20), 161 (24),
5
8
147 (43).
Superacid Cyclization of 1. A cooled (-78°C) solution of 1 (85 mg, 0.146 mmol) in 2-nitropropane (1.4 mL) was
stirred and treated with a solution cooled to the same temperature of fluorosulfonic acid (37 mg, 0.37 mmol) in 2-nitropropane
(0.1 mL). The reaction mixture was stirred at -78°C for 15 min and treated with Et N:hexane (1:1, 1.0 mL). After the usual
3
work up, the crude product (100 mg) was chromatographed over a SiO (4 g) column with gradient elution by petroleum
2
ether:AcOEt to afford (13E,17E)-12-phenylsulfonylbicyclogeranylfarnesol THP ether (8, 9 mg, 8%) and (13E,17E)-12-
phenylsulfonylbicyclogeranylfarnesol (9, 21 mg, 25%).
Compound 8, colorless liquid, C H SO .
36 54
4
IR spectrum (liquid film, ν, cm −1): 2927, 2854, 1446, 1378, 1304, 1146, 1086.
PMR spectrum (300 MHz, δ , ppm, J/Hz): 0.80 (3H, s, H -21), 0.87 (3H, s, H -23), 1.05 (3H, s, H -22), 1.52 (3H, s,
H
3
3
3
H -24), 1.57 (3H, s, H -20), 1.63 (3H, s, H -25), 3.15-3.30 (2H, m, H -5′′), 3.38 (1H, dd, J = 6.9, J = 11.2, H -19), 3.44 (1H,
3
3
3
2
1
2
A
dd, J = 3.8, J = 11.2, H -19), 3.60-3.67 (1H, m, H-12), 4.80-4.86 (1H, m, H-1′′), 5.21 (1H, t, J = 5.6, H-14), 5.32 (1H, m,
1
2
B
H-18), 7.54-7.88 (5H, m, Ar–H).
13
C NMR spectrum (75.5 MHz, δ , ppm): 15.5 (q, C-25), 16.7 (t, C-2), 19.6 (t, C-4′′), 19.7 (t, C-6), 20.1 (q, C-21),
C
20.4 (q, C-24), 21.1 (q, C-23), 24.4 (t, C-11), 26.7 (q, C-20), 24.5 (t, C-3′′), 26.8 (t, C-15), 29.5 (t, C-2′′), 33.0 (q, C-22), 33.1
(t, C-7), 33.2 (s, C-4), 34.9 (t, C-1), 38.8 (s, C-10), 45.5 (t, C-16), 46.3 (t, C-3), 50.8 (d, C-5), 52.3 (d, C-12), 59.7 (t, C-19),
63.3 (t, C-5′′), 97.1 (d, C-1′′), 120.4 (d, C-18), 127.7 (d, C-14), 128.5 (s, C-8), 129.1 (d, C-2′ and C-6′), 129.3 (d, C-3′ and
C-5′), 133.8 (s, C-9), 134.6 (s, C-13), 135.3 (s, C-17), 135.6 (d, C-4′), 139.8 (s, C-1′).
Compound 9, colorless liquid, C H SO .
31 46
3
IR spectrum (liquid film, ν, cm −1): 3449, 2931, 2856, 1447, 1380, 1304, 1145, 1085, 895.
271