HETEROCYCLES, Vol. 77, No. 1, 2009
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(600 MHz, C6D6) δ 7.86 (dd, J = 15.0, 12.1 Hz, 1 H), 6.82 (d, J = 9.0 Hz, 1 H), 6.74 (d, J = 9.0 Hz, 1 H),
6.45 (d, J = 12.1 Hz, 1 H), 6.00 (t, J = 12.1 Hz, 1 H), 5.84 (d, J = 15.0 Hz, 1 H), 5.21 (m, 1 H), 5.14-5.10
(m, 1 H), 3.82 (dd, J = 10.5, 5.1 Hz, 1 H), 3.62 (dd, J = 10.5, 6.0 Hz, 1 H), 3.28-3.24 (m, 1 H), 3.21-3.16
(m, 1 H), 2.37 (m, 1 H), 2.27 (s, 3 H), 2.20-2.17 (m, 1 H), 1.39 (s, 3 H), 1.03 (s, 9 H), 0.94 (s, 9 H), 0.14
13
(s, 6 H), 0.05 (s, 3 H), 0.03 (s, 3 H); C NMR (150 MHz, C6D6) δ 167.7, 154.3, 143.0, 140.3, 138.0,
132.8, 130.7, 129.2, 128.9, 128.8, 127.4, 122.7, 116.9, 72.1, 65.9, 43.1, 30.5, 30.4, 30.2, 26.0, 25.9, 18.4,
15.6, -4.2, -5.2, -5.3; HRMS (ESI) calcd for C31H50O4Si2Na (M+Na)+ 565.3145, found 565.3148.
TADA Reaction of 27. A solution of 27 (5.2 mg, 9.59 µmol) in 1,2,4-trichlorobenzene (1.0 mL) was
stirred at 160 °C for 10 h. Concentration and purification with PTLC (hexane/EtOAc, 8:1) gave 28 (2.7
mg, 50%) and 29 (1.9 mg, 35%). For 28: colorless solid; Rf = 0.23 (hexane/EtOAc, 7:1); [α]20D +69.7° (c
0.14, CH2Cl2); IR (CHCl3) 2930, 1717, 1601 cm-1; 1H NMR (400 MHz, C6D6) δ 6.81 (d, J = 7.2 Hz, 1 H),
6.73 (d, J = 7.2 Hz, 1 H), 5.69 (dt, J = 9.6, 2.4 Hz, 1 H), 5.58 (dt, J = 9.6, 2.4 Hz, 1 H), 4.18-4.14 (m, 1 H),
3.62 (dd, J = 11.4, 4.2 Hz, 1 H), 3.46 (dd, J = 11.4, 3.6 Hz, 1 H), 3.38-3.35 (m, 1 H), 2.99-2.97 (m, 1 H),
2.42 (dd, J = 15.6, 7.8 Hz, 1 H), 2.27 (dd, J = 15.6, 10.8 Hz, 1 H), 2.16 (s, 3 H), 2.11-1.97 (m, 2 H), 1.07
13
(s, 9 H), 0.99 (s, 9 H), 0.96-0.92 (m, 1 H), 0.70 (s, 3 H), 0.17 (s, 3 H), 0.16 (s, 3 H), 0.13 (s, 6 H); C
NMR (150 MHz, C6D6) δ 171.0, 153.1, 142.6, 137.2, 130.8, 128.4, 123.5, 121.4, 117.6, 76.8, 65.8, 48.8,
46.1, 43.4, 32.6, 32.5, 31.5, 30.2, 26.0, 25.9, 23.7, 18.5, 13.4, -4.2, -5.1, -5.3; HRMS (ESI) calcd for
C31H50O4Si2Na (M+Na)+ 565.3145, found 565.3130. For 29: colorless solid; Rf = 0.41 (hexane/EtOAc,
1
7:1); [α]20 –43.7° (c 0.10, CH2Cl2); IR (CHCl3) 2928, 1729, 1602 cm-1; H NMR (400 MHz, CDCl3) δ
D
6.92 (d, J = 7.8 Hz, 1 H), 6.62 (d, J = 7.8 Hz, 1 H), 5.89 (dt, J = 10.2, 3.0 Hz, 1 H), 5.59 (dt, J = 10.2, 2.4
Hz, 1 H), 4.64-4.60 (m, 1 H), 3.75-3.71 (m, 2 H), 3.69 (dd, J = 10.8, 4.8 Hz, 1 H), 3.13 (dd, J = 5.4, 3.0
Hz, 1 H), 2.82 (dd, J = 15.0, 7.8 Hz, 1 H), 2.67-2.50 (m, 1 H), 2.09 (s, 3 H), 1.95 (dd, J = 14.4, 4.2 Hz, 1
H), 1.71-1.65 (m, 1 H), 1.15 (s, 3 H), 1.02-0.95 (m, 1 H), 1.01 (s, 9 H), 0.91 (s, 9 H), 0.20 (s, 3 H), 0.19 (s,
3 H), 0.09 (s, 6 H); 13C NMR (150 MHz, CDCl3) δ 173.1, 158.9, 152.9, 142.3, 136.4, 132.9, 127.8, 120.8,
117.8, 77.1, 65.0, 48.5, 47.0, 43.5, 37.4, 37.0, 33.0, 32.0, 29.7, 29.5, 25.8, 25.7, 13.1, 0.0, -4.1, -5.3;
HRMS (ESI) calcd for C31H50O4Si2Na (M+Na)+ 565.3145, found 565.3132.
ACKNOWLEDGMENTS
This work was supported in part by a Grant-in-Aid for Creative Scientific Research (16GS0206) from the
Ministry of Education, Culture, Sports, Science and Technology, Japan.