G. Fraboulet et al. / Tetrahedron 65 (2009) 3953–3960
3959
resulting polymer was washed with absolute ethanol (6ꢂ30 mL)
and dried under vacuum (0.5 mbar) at 60 ꢁC for 6 h before solid state
MAS-NMR measurements and regeneration. The polymer was
obtained as awhite resin, and was found to be an Sn–Cl type polymer
MS (EI, 70 eV) m/z (I%): 280 (17), 209 (20), 196 (32), 181 (100), 81
(31), 67 (29), 57 (21), 55 (19), 43 (11).
IR (film, cmꢀ1): 3030, 2965–2802, 1652, 1180, 1081.
Anal. Calcd for C19H36O: C, 81.36; H, 12.94. Found: C, 81.29; H,
12.75.
containing 0.98 mmol of Sn–Cl g
.
ꢀ1 119Sn MAS-NMR:
d¼þ147 ppm.
Products distribution in 2,6-disubstituted dihydropyrans 4 and
7 were firmly characterized on the basis of their 1H NMR spectra.
Their isomeric distribution was determined by GC analysis of crude
reaction mixtures.
4.7.5. 2,6-cis-Di-(1-phenylethyl)-5,6-dihydro-2H-pyran 4e16,21
1H NMR (CDCl3)
d
(ppm): 7.30–7.15 (10H, m), 5.78 (1H, m), 5.60
(1H, m), 4.05 (1H, m), 3.49 (1H, m), 2.82 (4H, m), 1.91 (6H, m). 13C
NMR (CDCl3) (ppm): 142.5, 130.7, 128.8, 128.5, 125.9, 125.1, 74, 73,
d
4.7.1. 2,6-cis-Dipropyl-5,6-dihydro-2H-pyran 4a
37.4, 32, 31.7, 31.6. GC tR
17.77 min (ꢄ1%).
¼17.33 min (ꢃ99%); GC tR
¼
(cis)
(trans)
1H NMR (CDCl3)
d
(ppm): 5.71 (1H, br ddt, 3J¼10.4 and 4.2 Hz,
4J¼2.3 Hz), 5.45 (1H, br ddt, 3J¼10.4 and 4.2 Hz, 4J¼1.8 Hz), 4.05 (1H,
m, H), 3.45 (1H, ddt, 3J¼7.2 and 7 Hz),1.98 (2H, m),1.75–1.15 (8H, m),
MS (CI /NH3, 70 eV) m/z (I%): 310 (MþNHþ4 ), 293 (MþHþ).
IR (film, cmꢀ1): 3029, 2955–2804, 1655, 1182, 1087.
Anal. Calcd for C21H24O: C, 86.26; H, 8.27. Found: C, 86.23; H,
8.15.
0.95 (6H, t, 3J¼5.2 Hz). 13C NMR (CDCl3)
d
(ppm): 130.7, 124.6, 74.6,
72.7, 38.2, 37.8, 31.5, 18.8, 18.5, 14.1. GC tR (cis)¼4.84 min (>99%).
MS (CI/NH3, 70 eV) m/z (I%): 186 (MþNHþ4 ), 169 (MþHþ).
IR (film, cmꢀ1): 3027, 2956–2805, 1652, 1182, 1087.
Anal. Calcd for C11H20O: C, 78.51; H, 11.98. Found: C, 78.49; H,
11.95.
4.7.6. 1-(Trimethyl)silylhept-1-en-4-ol 5a
E-isomer: 1H NMR (CDCl3)
d
(ppm): 6.03 (1H, br dt, 3J¼6.8 and
18.6 Hz), 5.66 (1H, brdt, 3J¼18 Hz, 4J¼1.15 Hz), 3.55 (1H, m), 2.15 (2H,
m),1.35 (2H, m), 0.82 (3H, m), 0.13 (9H, s). 13C NMR (CDCl3)
d (ppm):
4.7.2. 2,6-Dihexyl-5,6-dihydro-2H-pyran 4b
144, 132, 71, 44, 41, 39, 18, 14, 0. GC tR (trans)¼5.59 min (79%).
cis-Isomer: 1H NMR (CDCl3)
d
(ppm): 5.77 (1H, br ddt, 3J¼10.6
Z-isomer: 1H NMR (CDCl3)
d
(ppm): 6.34 (1H, br dt, 3J¼7, 8, and
and 4.1 Hz, 4J¼2.3 Hz), 5.62 (1H, br ddt, 3J¼10.6 and 4.1 Hz,
4J¼1.76 Hz), 4.05 (1H, m, H), 3.47 (1H, ddt, 3J¼7.2 and 7 Hz), 1.98
(2H, 2ꢂddd, 2J¼5 Hz, 3J¼4.1 Hz, 4J¼2.3 Hz), 1.62–1.20 (10H, m),
21 Hz), 5.58 (1H, br dt, 3J¼14 Hz, 4J¼1.15 Hz), 3.55 (1H, m), 2.15 (2H,
m), 1.35 (2H, m), 0.82 (3H, m), 0.02 (9H, s). 13C NMR (CDCl3)
d
(ppm): 142, 132, 71, 45, 43, 39, 18, 14, ꢀ1. GC tR
¼5.82 min
(cis)
0.95–0.75 (6H, m). 13C NMR (CDCl3)
d
(ppm): 129.5,123, 74, 73, 35.5,
(21%).
34.5, 30.5, 28, 24.5, 21, 13. GC tR¼11.06 min (95%).
MS (EI, 70 eV) m/z (I%): 171 (15), 145 (70), 114 (26), 99 (100).
IR (film, cmꢀ1): 3353, 2955–2855, 1606, 1247, 1125, 837.
Anal. Calcd for C10H22OSi: C, 64.44; H, 11.90; Si, 15.07. Found: C,
64.23; H, 8.15; Si, 15.00.
trans-Isomer: 1H NMR (CDCl3)
d
(ppm): 5.74 (1H, br ddt, 3J¼10.1
and 4.6 Hz, 4J¼2.1 Hz), 5.60 (1H, br ddt, 3J¼10.1 and 4.6 Hz,
4J¼1.8 Hz), 4.04 (1H, m), 3.55 (1H, ddt, 3J¼8.1 and 8.4 Hz), 1.90–1.75
(2H, m), 1.61–1.13 (10H, m), 0.90–0.74 (6H, m). 13C NMR (CDCl3)
d
(ppm): 129, 122.3, 73.5, 70.1, 34.9, 32.9, 30, 27, 24.5, 21, 12.5. GC
4.7.7. 1-(Trimethylsilyl)dec-1-en-4-ol 5b16
tR¼11.50 min (5%).
E-isomer: 1H NMR (CDCl3)
d
(ppm): 5.96 (1H, br dt, 3J¼6.8
MS (EI, 70 eV) m/z (I%): 252 (8), 195 (19), 182 (35), 167 (100), 149
(12), 113 (22), 81 (45), 55 (55), 29 (38).
IR (film, cmꢀ1): 3029, 2955–2804, 1652, 1182, 1087.
Anal. Calcd for C17H32O: C, 80.88; H, 12.78. Found: C, 80.59; H,
12.85.
and 18.6 Hz), 5.71 (1H, br dt, 3J¼18.6 Hz, 4J¼1.15 Hz), 3.62 (1H,
m), 2.14 (2H, m), 1.48 (1H, d, 3J¼4.3 Hz), 1.50–1.21 (10H, m),
0.92–0.74 (3H, m), ꢀ0.3 (9H, s). 13C NMR (CDCl3)
134, 70.5, 45, 36.5, 31, 29, 25, 22, 14, ꢀ1. GC tR
d
(ppm): 142,
¼9.70 min
(trans)
(62%).
Z-isomer: 1H NMR (CDCl3)
d
(ppm): 6.28 (1H, br dt, 3J¼6.8 and
4.7.3. 2,6-Dicyclohexyl-5,6-dihydro-2H-pyran 4c21
14.7 Hz), 5.62 (1H, br dt, 3J¼14.7 Hz, 4J¼1.15 Hz), 3.62 (1H, m), 2.30
cis-Isomer: 1H NMR (CDCl3)
d
(ppm): 5.73 (1H, br ddt, 3J¼10.2
(2H, m), 1.48 (1H, d, 3J¼4.3 Hz), 1.50–1.21 (10H, m), 0.92–0.74 (3H,
and 7.5 Hz, 4J¼2.5 Hz), 5.59 (1H, br ddt, 3J¼10.2 and 7 Hz,
4J¼2.2 Hz), 3.72 (1H, m), 3.10 (1H, ddt, 3J¼7.3 Hz and 7 Hz),1.85 (2H,
m), 1.75–0.81 (20H, m), 1.45–0.30 (2H, m). 13C NMR (CDCl3)
m), 0.5 (9H, s). 13C NMR (CDCl3)
d (ppm): 144, 132, 71, 41, 36.5, 31,
29, 25, 22, 14, 0. GC tR (cis)¼9.90 min (38%).
MS (EI, 70 eV) m/z (I%): 227 (15), 114 (40), 99 (70), 73 (100), 43
(23).
d
(ppm): 129, 125.3, 79.2, 78, 42.9, 31.2, 29.7, 28.7, 28.3, 26.7, 26. GC
tR¼12.86 min (95%).
IR (film, cmꢀ1): 3353, 2955–2855, 1606, 1247, 1125, 837.
Anal. calcd for C13H28OSi: C, 68.35; H, 12.35; Si, 12.30. Found: C,
68.28; H, 12.15; Si, 12.00.
trans-Isomer: NMR 1H (CDCl3)
d (ppm): 5.78 (2H, m), 3.68 (1H,
dd, 3J¼8.6 and 8.5 Hz), 3.25 (1H, br dt, 3J¼8.3 and 5.1 Hz), 1.99 (2H,
m), 2.05–1.19 (20H, m), 0.90–0.82 (2H, m). 13C NMR (CDCl3)
d
(ppm): 128.4, 124.3, 76.5, 72.3, 42.6, 41.8, 29.9, 29.6, 28.3, 27.2,
4.7.8. 1-Cyclohexyl-4-(trimethylsilyl)but-3-en-1-ol 5c
26.5, 19.6. GC tR¼13.46 min (5%).
E-isomer: 1H NMR (CDCl3)
d
(ppm): 5.90 (1H, br dt, 3J¼6.8 and
MS (EI, 70eV) m/z (I%): 248 (35), 165 (100), 147 (26), 95 (18), 83
(34), 67 (26), 55 (25), 29 (8).
18.6 Hz), 5.64 (1H, br dt, 3J¼18 Hz, 4J¼1.2 Hz), 3.60 (1H, m), 2.07
(2H, m), 1.48 (1H, s), 1.52–0.65 (11H, m), ꢀ0.07 (9H, s). 13C NMR
IR (film, cmꢀ1): 3030, 2923–2792, 1652, 1188, 1087.
Anal. Calcd for C17H28O: C, 82.20; H, 11.36. Found: C, 82.09; H,
11.35.
(CDCl3) d (ppm): 143.2, 134.1, 74.3, 43, 41.6, 28.8, 27.8, 26.2, 26, 25.9,
ꢀ1.49. GC tR (trans)¼9.53 min (62%).
Z-isomer: 1H NMR (CDCl3)
d
(ppm): 6.20 (1H, br dt, 3J¼7.2 and
14 Hz), 5.55 (1H, brdt, 3J¼14 Hz, 4J¼1.2 Hz), 3.60 (1H, m), 2.14 (2H, m),
4.7.4. 2,6-cis-Diheptyl-5,6-dihydro-2H-pyran 4d
1.49 (1H, s),1.52–0.65 (11H, m), 0.00 (9H, s).13C NMR (CDCl3)
d (ppm):
1H NMR (CDCl3)
d
(ppm): 5.72 (1H, br ddt, 3J¼10.4 and 4 Hz,
144.8, 132.6, 74.9, 43, 37.6, 28.8, 27.8, 26.2, 26, 25.9, 0. GC tR (cis)
9.72 min (38%).
¼
4J¼2.3 Hz), 5.57 (1H, br ddt, 3J¼10.4 and 4 Hz, 4J¼1.8 Hz), 4.03 (1H,
m), 3.43 (1H, ddt, 3J¼7.2 and 6.9 Hz), 1.89 (2H, 2ꢂddd, 2J¼5 Hz,
3J¼4.3 Hz, 4J¼2.2 Hz), 1.55–1.13 (14H, m), 0.87–0.79 (6H, m). 13C
MS (EI, 70 eV) m/z (I%): 185 (40), 114 (23), 99 (100), 83 (15), 73
(55).
NMR (CDCl3)
28.5, 25.3, 22.7, 13. GC tR
13.46 min (<5%).
d
(ppm): 130.5, 124.4, 74.9, 73.8, 35.5, 31.9, 31.4, 29,
IR (film, cmꢀ1): 3385, 2925–2852, 1605, 1247, 1085, 837.
Anal. Calcd for C13H26OSi: C, 68.95; H, 11.57; Si, 12.40. Found: C,
68.78; H, 11.35; Si, 12.15.
¼12.83 min (ꢃ95%); GC tR
¼
(trans)
(cis)