2818
H.-S. Jeon et al.
PAPER
1H NMR: d = 0.85 (d, J = 6.0 Hz, 3 H), 0.86 (d, J = 6.0 Hz, 3 H),
0.87 (d, J = 6.4 Hz, 6 H), 0.98–1.87 (m, 27 H), 1.04 (s, 3 H), 1.24
(s, 3 H), 1.73 (s, 3 H), 1.97–2.06 (m, 2 H), 1.99 (s, 3 H), 2.02 (s, 3
H), 2.03 (s, 3 H), 2.10 (s, 3 H), 2.41 (s, 3 H), 2.59 (t, J = 6.6 Hz, 2
H), 6.09 (s, 1 H), 6.17 (A of ABq, JAB = 15.9 Hz, 1 H), 6.19 (d,
J = 11.2 Hz, 1 H), 6.30 (B of ABq, JAB = 15.9 Hz, 1 H), 6.39 (d,
J = 15.0 Hz, 1 H), 7.07 (dd, J = 15.0, 11.2 Hz, 1 H).
13C NMR: d = 11.8, 12.2, 12.9, 13.1, 14.0, 19.2, 19.6, 19.7, 19.7,
20.6, 21.0, 21.7, 22.6, 22.7, 23.9, 24.4, 24.8, 28.0, 29.0, 31.1, 32.7,
32.8, 33.1, 34.2, 37.3, 37.4, 37.4, 39.3, 39.6, 40.0, 74.9, 117.2,
117.4, 122.9, 125.1, 126.9, 128.9, 129.5, 130.1, 131.6, 135.0, 137.2,
137.6, 140.0, 140.4, 149.2, 154.8, 165.8.
1H NMR: d = 0.83 (s, 3 H), 1.04 (br s, 6 H), 1.22–1.81 (m, 12 H),
1.73 (s, 3 H), 1.84–1.95 (m, 2 H), 1.98–2.11 (m, 2 H), 2.02 (s, 3 H),
2.06 (s, 3 H), 2.13–2.36 (m, 3 H), 2.40 (s, 3 H), 2.82–2.94 (m, 2 H),
4.69 (dd, J = 9.0, 7.7 Hz, 1 H), 5.98 (s, 1 H), 6.17 (A of ABq,
JAB = 16.1 Hz, 1 H), 6.18 (d, J = 11.3 Hz, 1 H), 6.31 (B of ABq,
JAB = 16.1 Hz, 1 H), 6.36 (d, J = 15.0 Hz, 1 H), 6.83 (d, J = 2.6 Hz,
1 H), 6.86 (dd, J = 8.4, 2.6 Hz, 1 H), 7.07 (dd, J = 15.0, 11.3 Hz, 1
H), 7.28 (d, J = 8.4 Hz, 1 H).
13C NMR: d = 12.0, 12.9, 14.0, 19.2, 21.2, 21.7, 23.2, 26.0, 27.0,
27.5, 28.9, 29.5, 33.1, 34.2, 36.8, 38.2, 39.5, 42.8, 43.9, 49.7, 82.7,
117.3, 118.8, 121.7, 126.3, 129.0, 129.4, 130.1, 131.8, 134.8, 137.2,
137.5, 137.6, 138.0, 140.2, 148.4, 155.2, 165.8, 171.2.
HRMS (FAB+): m/z calcd for C49H77O3: 713.5873; found:
HRMS (FAB+): m/z calcd for C40H52O4: 596.3866; found:
713.5865.
596.3852.
Compound 1c
Compound 11 (Entry 1, Table 2)
Following the general procedure for 1b, the reaction of 10c (1.52 g,
2.56 mmol) and DBU (0.78 g, 5.12 mmol) in THF (20 mL) at r.t. for
1 h produced 1c.
To a stirred solution of C15 sulfone 3 (3.19 g, 9.3 mmol) in THF (30
mL) at –78 °C was added a solution of BuLi in hexane (1.6 M; 6.4
mL, 10.2 mmol). The mixture was stirred at that temperature for 30
min and a solution of 6 (1.97 g, 11.1 mmol) in THF was added. The
reaction mixture was stirred at –78 °C for 1 h, quenched with aq
HCl (1 M; 50 mL), extracted with Et2O, dried (Na2SO4), filtered,
and concd under reduced pressure. The crude product was purified
by SiO2 column chromatography to give the less polar diastereomer
11 (0.95 g, 2.16 mmol) and the more polar diastereomer 11 (1.91g,
4.33 mmol) in total 70% yield.
Yield: 1.05 g, 2.28 mmol (89%).
IR (KBr): 2957, 1726, 1607, 1580, 1485, 1360, 1220, 1119, 965,
772 cm–1.
1H NMR: d = 1.04 (s, 6 H), 1.33 (s, 9 H), 1.43–1.50 (m, 2 H), 1.57–
1.68 (m, 2 H), 1.81 (s, 3 H), 1.97–2.06 (m, 2 H), 2.02 (s, 3 H), 2.42
(s, 3 H), 3.78 (s, 3 H), 6.02 (br s, 1 H), 6.16 (A of ABq, JAB = 16.0
Hz, 1 H), 6.17 (d, J = 11.3 Hz, 1 H), 6.30 (B of ABq, JAB = 16.0 Hz,
1 H), 6.39 (d, J = 15.0 Hz, 1 H), 6.70–6.77 (m, 1 H), 6.90–6.97 (m,
2 H), 7.08 (dd, J = 15.0, 11.3 Hz, 1 H).
Data for the Less Polar Diastereomer 11
Rf 0.43 (3:2, EtOAc–hexanes).
1H NMR: d = 0.96 (s, 3 H), 0.98 (s, 3 H), 1.32 (s, 3 H), 1.42–1.48
(m, 2 H), 1.55–1.65 (m, 2 H), 1.66 (s, 3 H), 2.00 (t, J = 6.2 Hz, 2 H),
2.37 (s, 3 H), 4.50 (dd, J = 11.2, 2.9 Hz, 1 H), 5.18 (d, J = 11.2 Hz,
1 H), 5.58 (s, 1 H), 5.94 (br s, 1 H), 5.96 (A of ABq, JAB = 16.3 Hz,
1 H), 6.07 (B of ABq, JAB = 16.3 Hz, 1 H), 7.50–7.68 (m, 3 H),
7.80–7.83 (m, 2 H).
13C NMR: d = 12.9, 14.0, 19.2, 21.7, 28.9, 30.0, 33.1, 34.2, 34.6,
39.6, 55.4, 110.4, 113.7, 117.7, 124.7, 129.0, 129.4, 130.1, 131.8,
134.8, 137.2, 137.6, 140.2, 142.5, 142.6, 155.3, 156.6, 165.9.
HRMS (FAB+): m/z calcd for C31H43O3: 463.3212; found:
463.3216.
13C NMR: d = 12.3, 15.3, 19.1, 21.6, 28.8, 28.8, 32.9, 34.1, 39.4,
66.5, 81.6, 114.3, 119.5, 129.0, 129.1, 130.0, 130.1, 134.1, 135.3,
137.1, 138.0, 145.2, 166.0, 171.6.
Compound 1d
Following the general procedure for 1b, the reaction of 10d (0.53 g,
0.65 mmol) and DBU (0.22 g, 1.43 mmol) in THF (20 mL) at 50 °C
for 4 h produced 1d.
Data for the More Polar Diastereomer 11
Rf 0.30 (3:2, EtOAc–hexanes).
Yield: 0.40 g, 0.60 mmol (92%).
IR (KBr): 2935, 1707, 1608, 1583, 1358, 1238, 1153, 966, 759
cm–1.
IR (KBr): 2928, 1770, 1646, 1308, 1149 cm–1.
1H NMR: d = 0.96 (s, 3 H), 1.00 (s, 3 H), 1.42–1.48 (m, 2 H), 1.55–
1.63 (m, 2 H), 1.64 (s, 3 H), 1.71 (s, 3 H), 1.99 (t, J = 6.2 Hz, 2 H),
2.02 (s, 3 H), 4.35 (dd, J = 10.5, 1.7 Hz, 1 H), 4.74 (d, J = 10.5 Hz,
1 H), 5.79 (s, 1 H), 5.83 (d, J = 1.7 Hz, 1 H), 5.87 (A of ABq,
JAB = 16.1 Hz, 1 H), 6.16 (B of ABq, JAB = 16.1 Hz, 1 H), 7.28–7.67
(m, 3 H), 7.83–7.86 (m, 2H).
13C NMR: d = 13.1, 13.7, 19.0, 21.5, 28.7, 28.8, 32.8, 34.0, 39.3,
65.5, 80.9, 112.1, 118.6, 127.6, 128.6, 129.8, 130.0, 130.2, 134.1,
135.4, 136.9, 144.9, 165.3, 171.9.
1H NMR: d = 0.68 (s, 3 H), 0.80–2.08 (m, 32 H), 0.87 (d, J = 6.4 Hz,
6 H), 0.92 (d, J = 6.1 Hz, 3 H), 1.03 (s, 6 H), 1.56 (s, 3 H), 1.71 (s,
3 H), 2.00 (s, 3 H), 2.31–2.39 (m, 2 H), 2.35 (s, 3 H), 4.56–4.72 (m,
1 H), 5.38 (br s, 1 H), 5.75 (s, 1 H), 6.13 (d, J = 11.9 Hz, 1 H), 6.14
(A of ABq, JAB = 15.7 Hz, 1 H), 6.27 (B of ABq, JAB = 15.7 Hz, 1
H), 6.28 (d, J = 15.2 Hz, 1 H), 6.99 (dd, J = 15.2, 11.9 Hz, 1 H).
13C NMR: d = 11.9, 12.9, 13.8, 18.7, 19.2, 19.3, 21.0, 21.7, 22.5,
22.8, 23.8, 24.3, 28.0, 28.2, 28.9, 31.9, 31.9, 33.1, 34.2, 35.8, 36.2,
36.6, 37.1, 38.3, 39.5, 39.6, 39.8, 42.3, 50.1, 56.2, 56.7, 73.2, 119.0,
122.5, 128.6, 129.5, 129.9, 130.8, 135.3, 137.3, 137.7, 139.4, 139.9,
152.5, 166.5.
HRMS (FAB+): m/z calcd for C20H27O2 (C26H33SO4 – C6H6SO2):
299.2011; found: 299.2009.
HRMS (FAB+): m/z calcd for C47H72O2: 668.5532; found:
668.5527.
Compounds 12a and 12b (Entry 1, Table 2)
To a solution of 11 (a 1:2 stereoisomeric mixture, 1.69 g, 3.8 mmol)
in THF (20 mL) was added DBU (1.7 mL, 11.5 mmol). The reaction
mixture was stirred at r.t. for 5 h, diluted with Et2O, washed with aq
HCl (1 M), dried (Na2SO4), filtered, and concd under reduced pres-
sure. The crude product was purified by SiO2 column chromatogra-
phy to give 12a (0.08 g, 0.27 mmol, 7%) and 12b (0.81 g, 2.7 mmol,
71%).
Compound 1e
Following the general procedure for 1b, the reaction of 10e (0.28 g,
0.40 mmol) and DBU (0.12 g, 0.80 mmol) in THF (10 mL) at r.t. for
3 h produced 1e.
Yield: 0.18 g, 0.29 mmol (72%).
IR (KBr): 2928, 1728, 1578, 1491, 1355, 1240, 1124, 913, 743
cm–1.
Synthesis 2004, No. 17, 2813–2820 © Thieme Stuttgart · New York