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General Procedure:
A mixture of TMSCl (0.7 mL, 5.5 mmol) and Et3N (0.7 mL,
5.0 mmol) was centrifuged at 3000 rpm for 5 min. The supernatant
(0.64 mL, containing 2.5 mmol of TMSCl) was added to a mixture of
dried InCl3 (158 mg, 0.72 mmol) and In (82 mg, 0.72 mmol)
in MeCN (2 mL). To the stirred mixture was added a solution of 4d (100 mg, 0.36 mmol) in MeCN (3 mL) and
the reaction mixture was stirred at 10-30 ˚C for
3 h under ultrasonication. The stirred mixture was diluted with
sat. NH4Cl (4 mL), and the aqueous layer was extracted
with EtOAc (2 × 20 mL). Drying over MgSO4, concentration,
and silica gel chromatography (SiO2: 14 g; hexane-EtOAc,
10:1) afforded 5d (55 mg, 0.31 mmol, 80%)
and 6d (5.3 mg, 0.03 mmol, 7%).
<A NAME="RU05509ST-10">10</A>
2: IR (neat):
3400(br), 2940, 2859, 1702, 1448, 1255, 1051, 925, 844, 761 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 5.70-5.81
(m, 1 H), 5.08 (d, J = 16.8
Hz, 1 H), 5.04 (d, J = 11.6 Hz,
1 H), 2.28 (d, J = 7.6 Hz, 2
H), 1.62-1.58 (m, 4 H), 1.35-1.46 (m, 2 H), 1.26-1.30
(m, 4 H). ¹³C NMR (100 MHz, CDCl3): δ = 182.6,
133.3, 117.7, 47.1, 44.3, 33.4, 25.3, 22.9. MS (EI): m/z = 123,
168 [M+]. HRMS (EI): m/z [M+] calcd for
C10H16O2: 168.1151; found: 168.1126.
5d: IR (neat): 3200(br), 2981, 1744, 1700,
1467, 1367, 1243, 1162, 1039, 929, 686, 606 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 5.64 (dt, J = 16.8, 10.4 Hz, 1 H), 5.21
(dd, J = 10.4, 1.6 Hz, 1 H),
5.19 (dd, J = 16.8, 0.6 Hz,
1 H), 4.03-4.20 (m, 2 H), 2.77-2.82 (m, 1 H),
2.00 (s, 3 H), 1.17 (s, 6 H).
¹³C
NMR (75 MHz, CDCl3): δ = 183.4, 170.8,
134.0, 119.7, 63.9, 49.7, 43.2, 24.4, 20.2. MS (EI): m/z = 200 [M+].
HRMS (EI): m/z [M+] calcd
for C10H16O4: 200.1048; found: 200.1027.
8a: IR (neat): 2979, 1708, 1455, 1364,
1272, 1104, 923, 848, 737, 698, 605 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 7.21-7.35
(m, 5 H), 5.67 (dt, J = 17.8,
9.3 Hz, 1 H), 5.15-5.21 (m, 2 H), 4.47 (s, 2 H), 3.47 (dd, J = 15.9, 8.8 Hz, 2 H), 2.79
(dd, J = 15.9, 6.6 Hz, 1 H),
1.16 (s, 3 H), 1.13 (s, 3 H). ¹³C NMR (75
MHz, CDCl3): δ = 183.7, 138.2, 135.3,
128.3, 128.3, 127.5, 119.1, 72.9, 70.5, 50.7, 43.5, 24.8, 20.4.
MS (EI):
m/z = 248 [M+].
HRMS (EI): m/z [M+] calcd
for C15H20O3: 248.1413; found:
248.1397.
8b: IR (neat): 2930,
1703, 1470, 1389, 1256, 1103, 1004, 921, 837, 776, 666 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 5.69 (ddd, J = 16.8, 10.2, 9.9 Hz, 1 H),
5.17 (dd, J = 10.2,
1.9 Hz, 1 H), 5.15 (dd, J = 16.7,
1.9 Hz, 1 H), 3.68 (t, J = 5.4
Hz, 2 H), 2.56 (dt, J = 9.3,
6.0 Hz, 1 H), 1.19 (d, J = 7.1
Hz, 6 H), 0.88 (s, 9 H), 0.05 (s, 6 H). ¹³C
NMR (75 MHz, CDCl3): δ = 183.9, 135.4,
119.0, 63.7, 52.8, 43.2, 25.9, 20.4, 18.3, -5.6. MS (EI): m/z = 273 [M + H+].
HRMS (EI): m/z [M+] calcd for
C14H28O3Si: 272.1808; found: 272.1785.
8c: IR (neat): 2943, 1704, 1469,
1354, 1265, 1122, 1034, 908, 815, 685, 545 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 5.59-5.75
(m, 1 H), 5.17 (dd, J = 17.6,
1.7 Hz, 1 H), 5.16 (dd, J = 11.3,
2.2 Hz, 1 H), 4.59 (s, 2 H), 3.69-3.90 (m, 2 H), 3.29-3.55
(m, 2 H), 2.79 (dt, J = 6.9,
2.2 Hz, 1 H), 1.42-1.89 (m, 6 H), 1.17 (s, 3 H), 1.13 (s,
3 H). MS (EI): m/z = 243
[M + H+].
HRMS (EI): m/z [M+] calcd
for C13H22O4: 242.1518; found:
242.1518.
10a: IR (neat): 2980,
1698, 1470, 1413, 1281, 1184, 926, 742, 706, 513 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 7.20-7.31
(m, 5 H), 6.25 (dt, J = 17.6,
9.6 Hz, 1 H), 5.15 (dd, J = 10.9,
0.6 Hz, 1 H), 5.14 (dd, J = 17.5,
0.6 Hz, 1 H), 3.63 (d, J = 9.6
Hz, 1 H), 1.18 (s, 3 H), 1.13 (s, 3 H). ¹³C
NMR (75 MHz, CDCl3): δ = 183.9, 140.0,
136.6, 129.3, 128.0, 126.8, 117.8, 57.3, 46.7, 23.2, 21.8. MS (EI): m/z = 204 [M+]. HRMS
(EI): m/z [M+] calcd
for C13H16O2: 204.1150; found: 204.1146.
10b: IR (neat): 2979, 1702, 1611, 1513,
1469, 1250, 1180, 1037, 922, 832, 540 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 7.13 (d, J = 8.8 Hz, 2 H), 6.83 (d, J = 8.8 Hz, 2 H), 6.21 (dt, J = 17.6, 10.1 Hz, 1 H), 5.13
(d, J = 11.0 Hz, 1 H), 5.12
(dd, J = 15.9, 0.9 Hz, 1 H),
3.71 (s, 3 H), 3.59 (d, J = 9.6
Hz, 1 H), 1.17 (s, 3 H), 1.12 (s, 3 H). ¹³C
NMR (75 MHz, CDCl3): δ = 183.7, 158.4,
136.9, 132.0, 130.2, 117.5, 113.4, 56.5, 55.1, 46.8, 23.1, 21.8.
MS (EI): m/z = 234 [M+].
HRMS (EI): m/z [M+] calcd
for C14H18O3: 234.1255; found:
234.1237.
10c: IR (neat): 2980,
1707, 1489, 1404, 1276, 1076, 1011, 925, 828, 516 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 7.42 (d, J = 8.5 Hz, 2 H), 7.09 (d, J = 8.5 Hz, 2 H), 6.18 (dt, J = 16.8, 9.9 Hz, 1 H), 5.17
(dd, J = 11.2, 0.9 Hz, 1 H),
5.14 (dd, J = 16.7, 0.8 Hz,
1 H), 3.60 (d, J = 9.3 Hz, 1
H), 1.18 (s, 3 H), 1.12 (s, 3 H). ¹³C
NMR (75 MHz, CDCl3): δ = 183.6, 139.0,
136.0, 131.2, 130.9, 120.8, 118.3, 56.6, 46.6, 22.9, 22.0. MS (EI): m/z = 282 [M+].
HRMS (EI): m/z [M+] calcd for
C13H15
79BrO2: 282.0255;
found: 282.0270.
10e: IR (neat):
2981, 1706, 1471, 1274, 1167, 1030, 925, 874, 793, 602 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 7.35 (s,
1 H), 7.26 (s, 1 H), 6.30 (s, 1 H), 6.00 (dt, J = 17.6,
9.3 Hz, 1 H), 5.15 (d, J = 11.8
Hz, 1 H), 5.14 (d, J = 15.1
Hz,
1 H), 3.61 (d, J = 9.1
Hz, 1 H), 1.19 (s, 3 H), 1.14 (s, 3 H). ¹³C
NMR (75 MHz, CDCl3): δ = 183.7, 142.5,
140.1, 136.1, 123.5, 117.8, 110.8, 48.0, 29.7, 22.6, 22.2. MS (EI): m/z = 194 [M+].
HRMS (EI): m/z [M+] calcd
for C11H14O3: 194.0943; found:
194.0939.
12: IR (neat): 2974,
1709, 1473, 1409, 1383, 1241, 1201, 1162, 943, 557 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 5.12 (tt, J = 7.7, 1.4 Hz, 1 H), 2.26
(d, J = 7.7 Hz, 2 H), 1.72 (s,
3 H), 1.61 (s, 3 H), 1.19 (s, 6 H). ¹³C
NMR (75 MHz, CDCl3): δ = 184.7, 134.6,
119.6, 42.7, 38.4, 26.0, 24.5, 17.9. MS (EI): m/z = 156 [M+].
HRMS (EI): m/z [M+] calcd
for C9H16O2: 156.1151; found: 156.1131.
14: IR (neat): 2984, 1742, 1700, 1471,
1417, 1385, 1242, 1037, 921, 606, 452, 440 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 5.90 (dd, J = 17.4, 10.9 Hz, 1 H), 5.20
(dd, J = 10.9, 0.8 Hz, 1 H),
5.08 (dd, J = 17.3, 0.8 Hz,
1 H), 4.26 (d, J = 11.1 Hz,
1 H), 4.13 (d, J = 11.1 Hz,
1 H), 2.02 (s, 3 H), 1.20 (s, 3 H), 1.19 (s, 3 H), 1.16 (s, 3 H). ¹³C
NMR (75 MHz, CDCl
3
): δ = 182.8,
171.0, 139.5, 115.7, 68.1, 46.8, 44.4, 21.6, 20.8, 16.7. MS (EI): m/z = 214 [M+].
HRMS (EI): m/z [M+] calcd for
C11H18O4: 214.1205; found: 214.1197.
16: IR (neat): 2978, 1700, 1468, 1375,
1293, 1131, 1009, 915, 740, 553 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 5.98 (dd, J = 17.3, 11.0 Hz, 1 H), 5.04
(dd, J = 10.7, 1.1 Hz, 1 H), 5.00
(dd, J = 17.3, 1.4 Hz, 1 H),
1.16 (s, 6 H), 1.10 (s, 6 H). ¹³C NMR
(75 MHz, CDCl3): δ = 183.9, 144.4,
112.5, 47.8, 40.9, 22.9, 21.4. MS (EI): m/z = 156 [M+].
HRMS (EI): m/z [M+] calcd
for C9H16O2: 156.1150; found: 156.1142.
18: IR (neat): 2979, 1955, 1705, 1455,
1360, 1284, 1069, 851, 739, 699 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 7.23-7.38
(m, 5 H), 4.94 (t, J = 2.1 Hz,
2 H), 4.59 (s, 2 H), 4.13 (t, J = 1.9
Hz, 2 H), 1.38 (s, 6 H). ¹³C NMR (100
MHz, CDCl3): δ = 207.4, 182.0, 137.9,
128.3, 127.7, 127.5, 104.5, 78.1, 71.9, 68.8, 43.0, 24.9. MS (EI): m/z = 246 [M+].
HRMS (EI): m/z [M+] calcd
for C15H18O3: 246.1255; found:
246.1257.
20: IR (neat): 2929,
1702, 1469, 1367, 1279, 1149, 942, 859, 721, 619 cm-¹. ¹H
NMR (300 MHz, CDCl3): δ = 5.79 (dd,
J = 10.3, 3.2 Hz, 1 H), 5.53
(d, J = 9.9 Hz, 1 H), 2.46-2.60 (m,
1 H), 1.40-2.20 (m, 6 H), 1.26 (s, 6 H). MS (EI): m/z = 168 [M+].
HRMS (EI): m/z [M+] calcd
for C10H16O2: 168.1150; found:
168.1168.
22: IR (neat): 2928,
1732, 1469, 1370, 1225, 1131, 1080, 1043, 794, 642, 605 cm-¹. ¹H
NMR (300 MHz, CDCl3):
δ = 5.85
(s, 2 H), 5.26 (dd, J = 9.2,
2.9 Hz, 1 H), 4.42 (d, J = 2.3
Hz, 1 H), 4.25 (dd, J = 11.8,
2.7 Hz, 1 H), 4.17 (dd, J = 11.8,
5.5 Hz, 1 H), 3.74 (dt, J = 2.7, 3.1 Hz, 1 H), 2.09
(s, 3 H), 2.07 (s, 3 H), 1.21 (s, 3 H), 1.18 (s, 3 H). ¹³C
NMR (75 MHz, CDCl3): δ = 180.5, 171.2,
170.6, 128.6, 127.6, 78.7, 74.1, 65.4, 63.2, 46.3, 21.0, 21.7, 20.5.
MS (EI): m/z = 300 [M+].
