H.-C. Lin, H.-J. Wu / Tetrahedron 56 (2000) 341–350
347
(2CH), 119.06 (C), 103.14 (C), 86.35 (CH), 84.99 (CH),
53.34 (CH), 50.91 (CH), 47.92 (CH), 42.33 (CH), 38.08
(CH2), 35.35 (CH2), 31.29 (CH2), 26.82 (CH2), 25.98
(CH2), 22.79 (CH2), 22.77 (CH2), 21.60 (CH3), 15.19
(CH3), 13.93 (CH3); LRMS m/z (rel int) 450 (Mϩ, 8), 295
(100); HRMS (EI) calcd for C24H34O6S 450.2076, found
450.2071.
5-Methyl-3b-hydroxy-9b-tosyl-4,11-dioxatetracyclo[5.2.1.
15,8.02,6]undecane 14a. Highly viscous oil; IR (CHCl3)
1
3500–3300, 1610, 1380, 1100 cmϪ1; H NMR (300 MHz,
CDCl3) d 7.79 (d, J8.1 Hz, 2H), 7.35 (d, J8.1 Hz, 2H),
5.35 (s, 1H), 4.61 (s, 1H), 4.20 (d, J4.5 Hz, 1H), 2.89–2.87
(m, 2H), 2.60–2.54 (m, 3H), 2.44 (s, 3H), 2.02 (d,
J11.1 Hz, 1H), 1.59 (d, J11.1 Hz, 1H), 1.54 (s, 3H);
13C NMR (75 MHz, CDCl3, DEPT) d 144.92 (C), 133.79
(C), 129.97 (2CH), 127.69 (2CH), 118.22 (C), 98.04 (CH),
86.48 (CH), 83.70 (CH), 52.83 (CH), 51.14 (CH), 48.02
(CH), 42.78 (CH), 35.53 (CH2), 25.45 (CH3), 21.65 (CH3);
LRMS m/z (rel int) 352 (Mϩ, 4), 197 (100); HRMS (EI)
calcd for C17H20O6S 352.0980, found 352.0987.
5-Methyl-9b-tosyl-3-oxo-4,11-dioxatetracyclo[5.2.1.15,8.02,6]
undecane 13a. Highly viscous liquid; 88% yield; IR
;
(CHCl3) 1775, 1610, 1380, 1100 cmϪ1 1H NMR
(300 MHz, CDCl3) d 7.80 (d, J8.1 Hz, 2H), 7.36
(d, J8.1 Hz, 2H), 4.46–4.45 (m, 1H), 4.32 (s, 1H), 3.06–
3.00 (m, 3H), 2.74–2.72 (m, 1H), 2.46 (s, 3H), 2.17 (d,
J11.4 Hz, 1H), 1.78 (d, J11.4 Hz, 1H), 1.59 (s, 3H);
13C NMR (75 MHz, CDCl3, DEPT) d 173.58 (CO),
145.37 (C), 132.85 (C), 130.14 (2CH), 127.88 (2CH),
116.80 (C), 87.19 (CH), 83.25 (CH), 51.20 (CH), 46.94
(2CH), 43.94 (CH), 36.87 (CH2), 23.57 (CH3), 21.68
(CH3); LRMS m/z (rel int) 350 (Mϩ, 3), 195 (100); HRMS
(EI) calcd for C17H18O6S 350.0824, found 350.0828.
5-n-Butyl-3b-hydroxy-9b-tosyl-4,11-dioxatetracyclo[5.2.1.
15,8.02,6]undecane 14b. Highly viscous oil; 83% yield; IR
(CHCl3) 3500–3300, 1610, 1380, 1100 cmϪ1 1H NMR
;
(300 MHz, CDCl3) d 7.80 (d, J8.1 Hz, 2H), 7.35
(d, J8.1 Hz, 2H), 5.36 (s, 1H), 4.60 (s, 1H), 4.21
(d, J4.8 Hz, 1H), 2.95-2.77 (m, 3H), 2.58–2.54 (m, 2H),
2.44 (s, 3H), 2.02 (d, J11.4 Hz, 1H), 1.90–1.62 (m, 2H),
1.59 (d, J11.4 Hz, 1H), 1.35–1.23 (m, 4H), 0.88 (t,
J6.9 Hz, 3H); 13C NMR (75 MHz, CDCl3, DEPT) d
144.88 (C), 133.81 (C), 129.97 (2CH), 127.70 (2CH),
120.57 (C), 97.92 (CH), 86.25 (CH), 83.85 (CH), 52.60
(CH), 49.37 (CH), 48.24 (CH), 42.84 (CH), 37.18 (CH2),
35.59 (CH2), 26.51 (CH2), 22.71 (CH2), 21.66 (CH3), 13.95
(CH3); LRMS m/z (rel int) 394 (Mϩ, 6), 239 (100); HRMS
(EI) calcd for C20H26O6S 394.1450, found 394.1456.
5-n-Butyl-9b-tosyl-3-oxo-4,11-dioxatetracyclo[5.2.1.15,8.02,6]
undecane 13b. Highly viscous liquid; 90% yield; IR
;
(CHCl3) 1775, 1610, 1380, 1100 cmϪ1 1H NMR
(300 MHz, CDCl3) d 7.80 (d, J8.1 Hz, 2H), 7.37
(d, J8.1 Hz, 2H), 4.48–4.46 (m, 1H), 4.32 (s, 1H),
3.04–2.94 (m, 3H), 2.73–2.71 (m, 1H), 2.46 (s, 3H), 2.17
(d, J11.7 Hz, 1H), 1.85–1.66 (m, 3H), 1.36–1.30 (m, 4H),
0.89 (t, J7.2 Hz, 3H); 13C NMR (75 MHz, CDCl3, DEPT)
d 173.70 (CO), 145.34 (C), 132.85 (C), 130.13 (2CH),
127.87 (2CH), 118.91 (C), 87.02 (CH), 83.85 (CH), 49.57
(CH), 47.14 (CH), 46.63 (CH), 43.95 (CH), 36.87 (CH2),
36.10 (CH2), 25.56 (CH2), 22.45 (CH2), 21.67 (CH3),13.84
(CH3); LRMS m/z (rel int) 392 (Mϩ, 4), 237 (100); HRMS
(EI) calcd for C20H24O6S 392.1293, found 392.1298.
5-n-Octyl-3b-hydroxy-9b-tosyl-4,11-dioxatetracyclo-
[5.2.1.15,8.02,6]undecane 14c. Highly viscous oil; 85%
1
yield; IR (CHCl3) 3500–3300, 1610, 1380, 1100 cmϪ1; H
NMR (300 MHz, CDCl3) d 7.79 (d, J8.1 Hz, 2H), 7.35 (d,
J8.1 Hz, 2H), 5.36 (s, 1H), 4.60 (s, 1H), 4.21 (d,
J4.8 Hz, 1H), 2.90–2.82 (m, 3H), 2.58–2.55 (m, 2H),
2.45 (s, 3H), 2.02 (d, J11.4 Hz, 1H), 1.78–1.70 (m, 2H),
1.59 (d, J11.4 Hz, 1H), 1.40–1.18 (m, 12H), 0.87 (t,
J6.9 Hz, 3H); 13C NMR (75 MHz, CDCl3, DEPT) d
144.89 (C), 133.77 (C), 129.96 (2CH), 127.69 (2CH),
120.56 (C), 97.90 (CH), 86.24 (CH), 83.84 (CH), 52.57
(CH), 49.35 (CH), 48.24 (CH), 42.82 (CH), 38.13 (CH2),
35.59 (CH2), 31.81 (CH2), 29.63 (CH2), 29.44 (CH2), 29.19
(CH2), 24.37 (CH2), 22.62 (CH2), 21.66 (CH3), 14.09 (CH3);
LRMS m/z (rel int) 450 (Mϩ, 2), 175 (100); HRMS (EI)
calcd for C24H34O6S 450.2076, found 450.2071.
5-n-Octyl-9b-tosyl-3-oxo-4,11-dioxatetracyclo[5.2.1.15,8.02,6]
undecane 13c. Highly viscous liquid; 92% yield; IR
;
(CHCl3) 1775, 1610, 1380, 1100 cmϪ1 1H NMR
(300 MHz, CDCl3) d 7.79 (d, J8.1 Hz, 2H), 7.36
(d, J8.1 Hz, 2H), 4.48–4.46 (m, 1H), 4.32 (s, 1H), 3.03–
2.94 (m, 3H), 2.74–2.72 (m, 1H), 2.45 (s, 3H), 2.17 (d,
J11.4 Hz, 1H), 1.85–1.74 (m, 3H), 1.40–1.22 (m, 12H),
0.87 (t, J6.6 Hz, 3H); 13C NMR (75 MHz, CDCl3, DEPT)
d 173.73 (CO), 145.35 (C), 132.85 (C), 130.13 (2CH),
127.87 (2CH), 118.91 (C), 87.02 (CH), 83.36 (CH), 49.56
(CH), 47.13 (CH), 46.62 (CH), 43.94 (CH), 36.87 (CH2),
36.40 (CH2), 31.75 (CH2), 29.51 (CH2), 29.31 (CH2), 29.09
(CH2), 23.46 (CH2), 22.59 (CH2), 21.68 (CH3), 14.07 (CH3);
LRMS m/z (rel int) 448 (Mϩ, 5), 293 (100); HRMS (EI)
calcd for C24H32O6S 448.1919, found 448.1912.
General procedure for the reaction of 12a,b and 14a–c
with potassium hydride in dry THF. Formation of
trioxa-cages 16a–e. To a solution of 12b (0.090 g,
0.20 mmol) in dry THF (20 mL) was added KH (0.10 g,
2.5 mmol) at 0ЊC. The reaction mixture was stirred at 0ЊC
for 2 h. To this reaction mixture was dropwise added H2O
(5 mL) at 0ЊC to destroy the unreacted KH. After addition of
saturated NH4Cl (10 mL) and extraction with ether
(4×30 mL), the organic layer was washed with brine,
dried over MgSO4, and evaporated, and the residue was
purified by column chromatography to give the diacetal
trioxa-cage compound 16b in 86% yield. Compounds 16a
and 16c–e have been prepared with a different method.16a
General procedure for the reduction of 13a–c with
sodium borohydride in methanol. To a solution of 13a
(0.070 g, 0.20 mmol) in methanol (20 mL) was added
sodium borohydride (0.038 g, 1.0 mmol) at 0ЊC. The
reaction mixture was stirred at 25ЊC for 1 h. After addition
of saturated NH4Cl (20 mL) and extraction with ether
(4×30 mL), the organic layer was washed with brine,
dried over MgSO4, and evaporated, and the residue was
purified by column chromatography to give the hemiacetal
14a in 80% yield.
4,6-Di-n-butyl-3,5,7-trioxapentacyclo[7.2.1.02,8.04,11.06,10]-
dodecane 16b. White solid; mp 116–117ЊC; IR (CHCl3)