H. Shi et al. / Tetrahedron 57 &2001) 9335±9341
9339
1605, 1497 cm21. 1H NMR 2250 MHz, CDCl3) d: 0.99 23H,
t, J6.9 Hz), 1.38±1.72 24H, m), 1.90±2.05 22H, m), 2.08
21H, s), 2.46 21H, d, J6.9 Hz), 2.63 21H, dd, J6.9 Hz),
4.22 21H, s), 5.00 21H, s), 5.42 21H, d, J6.9 Hz), 6.30 21H,
m), 6.40 21H, m), 7.29±7.43 25H, m). 13C NMR 263 MHz,
CDCl3) d: 13.9, 22.9, 26.0, 35.9, 49.4, 54.0, 78.5, 78.8,
105.2, 126.5, 127.3, 128.0, 137.3, 137.5, 138.2. ESMS m/z
2relative intensity): 595 22MNa1, 28), 309 2MNa1, 100).
HRESMS: Calcd for C18H23O3Na1: 309.1467. Found:
309.1475. Anal. calcd for C18H22O3: C, 75.50; H, 7.74.
Found: C, 75.23; H, 7.79.
29.7, 47.0, 55.1, 77.0, 77.8, 80.0, 104.6, 126.6, 128.0, 137.5,
137.6, 141.5. ESMS m/z 2relative intensity): 309 2MNa1,
100). HRESMS: Calcd for C18H22O3Na1: 309.1467.
Found: 309.1465.
4.2.6. ,1Sp,2Rp,3Rp,5Sp,6Sp,7Rp)-4,10-Dioxa-3-phenyl-5-
butyltricyclo[5.2.1.02,6]-dec-8-en-3-ol
18a.
Prepared
following the general procedure by addition of commercial
phenyllithium in ether/cyclohexane to lactone 12. Yield
86%; colorless liquid mixture of diastereomers 285/15).
1
Major product: H NMR 2200 MHz, C6D6) d: 0.93 23H, t,
J6.9 Hz), 1.15±1.56 26H, m), 1.84 21H, dd, J7.7 Hz),
2.36 21H, d, J7.7 Hz), 3.71 21H, q, J6.8 Hz), 4.17 21H,
s), 4.77 21H, d, J1.3 Hz), 5.26 21H, s), 5.57 21H, m), 5.78
4.2.2. ,1Sp,2Rp,3Rp,5Rp,6Sp,7Rp)-4,10-Dioxa-3,5-diphenyl-
tricyclo[5.2.1.02,6]-dec-8-en-3-ol 14. Prepared following
the general procedure by addition of commercial phenyl-
lithium in ether/cyclohexane to lactone 9. Yield 85%; color-
less solid. mp 133±1358C. IR 2KBr): 3350, 3064, 3023,
1
21H, m), 7.07±7.29 28H, m), 7.78±7.92 22H, m). H NMR
2250 MHz, CDCl3) d: 0.96 23H, t, J6.9 Hz), 1.31±1.56
24H, m), 1.64±1.93 22H, m), 2.36 21H, dd, J7.7, 7.6 Hz),
2.67 21H, d, J7.7 Hz), 3.89 21H, q, J6.8 Hz), 4.75 21H,
s), 5.07 21H, d, J1.3 Hz), 5.11 21H, s), 6.32 21H, m), 6.48
21H, m), 7.30±7.43 26H, m), 7.60±7.68 22H, m).
3003, 2968, 1496, 1447 cm21
.
1H NMR 2250 MHz,
CDCl3) d: 2.62±2.76 22H, m), 4.11 21H, s), 4.29 21H, s),
5.53 21H, d, J6.7 Hz), 6.26 22H, s), 7.31±7.59 28H, m),
7.73±7.81 22H, m). 13C NMR 263 MHz, CDCl3) d: 49.6,
56.8, 78.8, 78.9, 79.9, 105.1, 126.5, 126.7, 127.4, 128.2,
137.5, 137.6, 138.2, 141.0. ESMS m/z 2relative intensity):
329 2MNa1, 100). HRESMS: Calcd for C20H18O3Na1:
329.1154. Found: 329.1153.
4.3. General procedure for the reduction of lactols 13±
15, 16a, 17, 18a
To a solution of the lactol 21 mmol) in 1,1,1-tri¯uoroethanol
25 mL) at 220, 2258C wasadded NaBH 3CN 23 mmol). The
suspension was stirred for 5 min and was added dropwise
dichloroacetic acid. The solution was stirred for 1 h. The
mixture was quenched by a saturated solution of NaHCO3
25 ml), extracted with ether 23£10 mL). The organic phase
4.2.3.
,1Sp,2Rp,3Rp,5Sp,6Sp,7Rp)-4,10-Dioxa-3-butyl-5-
phenyltricyclo[5.2.1.02,6]-dec-8-en-3-ol 15. Prepared
following the general procedure by addition of commercial
butyllithium in hexane to lactone 10. Yield 54%; colorless
liquid. IR 2®lm, NaCl): 3491, 3065, 3029, 2992, 2954, 2866,
1605, 1496 cm21. 1H NMR 2200 MHz, CDCl3) d: 1.03 23H,
t, J7.0 Hz), 1.24±1.68 26H, m), 1.80±2.00 22H, m), 2.52
21H, dd, J8.7, 7.7 Hz), 2.68 21H, d, J8.7 Hz), 4.69 21H,
d, J7.6 Hz), 4.73 21H, s), 4.86 21H, s), 4.98 21H, s), 6.40
22H, s), 7.29±7.50 25H, m). 13C NMR 250 MHz, CDCl3) d:
13.9, 22.8, 26.1, 39.1, 54.3, 57.1, 79.2, 80.3, 80.4, 104.0,
126.0, 127.7, 128.4, 135.7, 137.7, 141.0. ESMS m/z 2relative
intensity): 309 2MNa1, 100). HRESMS: Calcd for
C18H22O3Na1: 309.1467. Found: 309.1468. Anal. calcd for
C18H22O3: C, 75.50; H, 7.74. Found: C, 75.46; H, 7.58.
wasdried over MgSO , and concentrated in vacuo. The
4
residue was puri®ed by chromatography on silica gel
2eluent: petroleum ether/AcOEt 90/10).
4.3.1.
,1Sp,2Rp,3Sp,5Rp,6Sp,7Rp)-4,10-Dioxa-3-butyl-5-
phenyltricyclo[5.2.1.02,6]-dec-8-en 19. Prepared from
lactol 13. Yield 90% or from lactol 17. Yield 71%; colorless
oil. IR 2®lm, NaCl): 3005, 2955, 2858, 1607, 1494,
1454 cm21. H NMR 2250 MHz, CDCl3) d: 0.97 23H, t,
1
J6.9 Hz), 1.35±1.60 24H, m), 1.70±2.04 22H, m), 2.38
21H, dd, J6.8 Hz), 2.50 21m, dd, J6.8 Hz), 3.47 21H,
dt, J7.0±6.3 Hz), 4.28 21H, s), 4.93 21H, d, J6.6 Hz),
5.06 21H, s), 6.27 21H, m), 6.38 21H, m), 7.28±7.44 25H,
m). 13C NMR 263 MHz, CDCl3) d: 14.0, 22.8, 28.9, 30.0,
48.7, 50.8, 77.8, 78.9, 79.2, 80.9, 126.6, 127.1, 128.0, 137.6,
138.9. ESMS m/z 2relative intensity): 593 2100), 293
2MNa1, 74). HRESMS: Calcd for C18H22O2Na1:
293.1518. Found: 293.1529.
4.2.4. ,1Sp,2Rp,3Rp,5Sp,6Sp,7Sp)-4,10-Dioxa-3,5-diphenyl-
tricyclo[5.2.1.02,6]-dec-8-en-3-ol 16a. Prepared following
the general procedure by addition of commercial phenyl-
lithium in ether/cycohexane to lactone 10. Yield 68%;
colorless liquid mixture of diastereomers 285/15). Major
adduct: 1H NMR 2250 MHz, C6D6) d: 2.21 21H, dd,
J7.7 Hz, 2.48 21H, d, J7.7 Hz), 4.33 21H, s), 4.74 21H,
d, J7.7 Hz), 4.78 21H, s), 5.32 21H, s), 5.53 21H, m), 5.64
21H, m), 7.18±7.37 28H, m), 7.95 22H, m).
4.3.2. ,1Sp,2Rp,3Sp,5Rp,6Sp,7Rp)-4,10-Dioxa-3,5-diphenyl-
tricyclo[5.2.1.02,6]-dec-8-en 20. Yield 90%; colorless solid.
mp 1348C. IR 2KBr): 3008, 2967, 2921, 2852, 1604, 1494,
4.2.5. ,1Sp,2Rp,3Rp,5Rp,6Sp,7Rp)-4,10-Dioxa-3-phenyl-5-
1
1454 cm21. H NMR 2250 MHz, CDCl3) d: 2.63 22H, m),
butyltricyclo[5.2.1.02,6]-dec-8-en-3-ol
17.
Prepared
4.35 22H, s), 5.15 22H, m), 6.26 22H, s), 7.30±7.45 26H, m),
7.57 24H, m). 13C NMR 263 MHz, CDCl3) d: 51.0, 78.9,
81.2, 126.7, 127.3, 128.2, 137.9, 138.8. ESMS m/z 2relative
intensity): 313 2MNa1, 100). HRESMS: Calcd for
C20H18O2Na1: 313.1204. Found: 313.1211. Anal. calcd for
C20H18O2: C, 82.73; H, 6.25. Found: C, 82.49; H, 6.29.
following the general procedure by addition of commercial
phenyllithium in ether/cyclohexane to lactone 11. Yield
71%; colorless liquid. IR 2®lm, NaCl): 3273, 3085, 3070,
2999, 2934, 2874, 1687, 1606, 1492 cm21 1H NMR
.
2250 MHz, CDCl3) d: 0.98 23H, t, J6.9 Hz), 1.36±1.55
24H, m), 1.70±2.00 22H, m), 2.46±2.57 22H, m), 4.03
21H, d, J1.3 Hz), 4.14 21H, q, J6.8 Hz), 5.01 21H, s),
6.26 21H, m), 6.37 21H, m), 7.32±7.44 23H, m), 7.57±7.66
22H, m). 13C NMR 263 MHz, CDCl3) d: 14.2, 23.0, 28.7,
4.3.3. ꢀ1Sp; 2Rp; 3Sp; 5Sp; 6Sp; 7Rp- and ,1Sp; 2Rp; 3Rp;
5Sp; 6Sp; 7Rp)-4,10-Dioxa-3-butyl-5-phenyltricyclo-
[5.2.1.02,6]-dec-8-en 21 and 24. Following the general