K. Benda, W. Regenhardt, E. Schaumann, G. Adiwidjaja
FULL PAPER
(film): ν = 3068, 2956, 1733, 1429, 1252, 1120, 1084, 1021, 871, 2 C), 126.5 (+), 111.4 (o), 110.4 (o), 110.3 (o), 108.6 (o), 72.4 (+),
˜
829, 701 cm–1. H NMR (400 MHz): δ = 7.96 (m, 1 H), 7.64 (m, 1 71.5 (o), 53.6 (o), 44.0 (–), 43.1 (o), –0.86 (+), –1.54 (+) ppm. MS
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H), 7.60 (m, 1 H), 7.40 (m, 4 H), 7.31 (m, 1 H), 7.22 (m, 1 H), 6.75
(d, J = 3.1 Hz, 1 H), 5.32 (d, J = 3.1 Hz, 1 H), 3.91 (m, 2 H), 3.78
(s, 3 H), 3.67 (m, 2 H), –0.27 (s, 3 H), –1.0 (s, 3 H) ppm. 13C NMR
(100 MHz): δ = 166.2 (o), 141.0 (o), 137.9 (+), 137.2 (o), 134.9 (o),
134.4 (o), 133.6 (+), 133.0 (+), 129.9 (+), 128.0 (+), 127.9 (+), 127.3
(+), 126.4 (+), 65.2 (+), 62.2 (o), 51.2 (+), 44.4 (–), 43.6 (–), –0.83
(+), –1.1 (+) ppm. MS (EI): m/z = 428, 393, 367, 335, 307, 290, 262,
233, 202, 135, 107, 91, 51. HRMS (EI): calcd. for C22H24O3S2Si:
428.0936; found 428.0929.
( E S I ) : m / z = 4 9 5 [ M + N a ] + . H R M S ( E I ) : c a l c d . fo r
C24H20N4OS2Si: 472.0848; found 472.0848.
Cycloaddition Reactions of Alkoxide 3d. General Procedure: A solu-
tion of ketone 5 (208 mg, 1 mmol) in dry THF (5 mL) was treated
with diisobutylaluminium hydride (1 in hexanes, 1.1 mL,
1.1 mmol) at –5 °C. The reaction was complete after 10 min and
dienophile 4, 14, 16 or 18 (1.1 mmol) was added. The resulting
mixture was warmed to room temp. and stirred for 10 h. Saturated
sodium potassium tartrate (10 mL) and Et2O (10 mL) were added
and the mixture was vigorously stirred for 20 min. The aqueous
phase was separated and extracted with Et2O (3ϫ5 mL). The com-
bined organic layers were washed with brine (10 mL) and dried.
Removal of the solvent in vacuo followed by flash chromatography
(PE/EtOAc, 2:1) gave products 2a,b, 15b, 17a–d, or 19.
Dimethyl 4Ј-{[Dimethyl(phenyl)silyl]oxy}-4ЈH-spiro[1,3-dithiolane-
2,1Ј-naphthalene]-2Ј,3Ј-dicarboxylate (9d): Yield 194 mg (40 %);
m.p. 107–108 °C. IR (film): ν = 3070, 2949, 1722, 1427, 1368, 1263,
˜
1119, 1016, 962, 889, 831, 701 cm–1. 1H NMR (400 MHz): δ = 7.97
(dd, J = 8.0, 1.2 Hz, 1 H), 7.54 (m, 2 H), 7.35 (m, 4 H), 7.17 (dt,
J = 7.6, 1.2 Hz, 1 H), 7.04 (dd, J = 7.6, 1.4 Hz, 1 H), 5.75 (s, 1 H),
3.83 (s, 3 H), 3.71 (m, 2 H), 3.64 (s, 3 H), 3.59 (m, 2 H), 0.36 (s, 3
H), 0.35 (s, 3 H) ppm. 13C NMR (100 MHz): δ = 167.1 (o), 165.5
(o), 147.9 (o), 140.9 (o), 138.0 (o), 134.8 (o), 133.5 (+), 131.0 (o),
129.4 (+), 128.4 (+), 128.3 (+), 128.2 (+), 127.6 (+), 127.4 (+), 65.8
(+), 63.5 (o), 52.2 (+), 52.1 (+), 44.0 (–), 42.4 (–), –0.28 (+), –1.1
(+) ppm. MS (EI): m/z = 486, 471, 458, 408, 398, 367, 348, 334,
316, 262, 233, 195, 135, 107, 61. HRMS (EI): calcd. for
C24H26O5S2Si: 486.0991; found 486.0990.
Methyl 4Ј-Hydroxy-4ЈH-spiro[1,3-dithiolane-2,1Ј-naphthalene]-3Ј-
carboxylate (2a): Yield 188 mg (64%); m.p. 101–102 °C. IR (film):
ν = 3485, 2950, 2922, 1710, 1650, 1484, 1437, 1278, 1250, 1220,
˜
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1126, 1027, 1007, 965, 911, 762, 733 cm–1. H NMR (400 MHz): δ
= 7.97 (d, J = 7.7 Hz, 1 H), 7.55 (d, J = 7.4 Hz, 1 H), 7.34 (m, 2
H), 7.20 (s, 1 H), 5.49 (s, 1 H), 3.87 (s, 3 H), 3.73 (m, 2 H), 3.63
(m, 2 H), 3.47 (br. s, 1 H) ppm. 13C NMR (100 MHz): δ = 167.6
(o), 142.1 (+), 135.3 (o), 135.1 (o), 130.0 (+), 128.6 (+), 128.4 (+),
128.3 (+), 123.6 (o), 63.0 (+), 62.6 (o), 52.2 (+), 42.1 (–), 41.9 (–
) ppm. MS (CI): m/z = 294, 276, 245, 219, 187, 145, 128. HRMS
(EI): calcd. for C14H14O3S2: 294.0384; found 294.0388.
12Ј-{[Dimethyl(phenyl)silyl]oxy}-11aЈ,12Ј-dihydro-5ЈaH-spiro[1,3-di-
thiolane-2,5Ј-tetracene]-6Ј,11Ј-dione (11b): Yield 108 mg (22%). IR
(film): ν = 3068, 2958, 1771, 1694, 1595, 1427, 1255, 1118, 1051,
˜
1
982, 832 cm–1. H NMR (400 MHz): δ = 8.11 (m, 1 H), 8.01 (dd,
Dimethyl 4Ј-Hydroxy-4ЈH-spiro[1,3-dithiolane-2,1Ј-naphthalene]-
2Ј,3Ј-dicarboxylate (2b): Yield 264 mg (75%); m.p. 135–136 °C. IR
J = 8.0, 1.0 Hz, 1 H), 7.87 (m, 1 H), 7.63 (m, 2 H), 7.25 (m, 4 H),
7.16 (dd, J = 8.0, 1.0 Hz, 2 H), 6.95 (dt, J = 7.5, 1.2 Hz, 1 H), 6.60
(d, J = 7.5 Hz, 1 H), 5.11 (d, J = 3.5 Hz, 1 H), 4.18 (dd, J = 5.0,
3.5 Hz, 1 H), 4.02 (d, J = 5.0 Hz, 1 H), 3.65, 3.48, 3.34, 3.16 (m, 1
H), –0.23, –0.31 (s, 3 H) ppm. 13C NMR (100 MHz): δ = 197.0 (o),
195.1 (o), 139.1 (o), 138.8 (o), 136.6 (o), 135.6 (o), 134.0 (+), 133.8
(o), 133.4 (+), 132.7 (+), 129.7 (+), 129.5 (+), 129.3 (+), 129.0 (+),
127.8 (+), 127.7 (+), 127.4 (+), 126.5 (+), 125.6 (+), 70.1 (+), 67.3
(o), 59.9 (+), 56.3 (+), 42.9 (–), 39.6 (–), –2.1 (+), –2.3 (+) ppm.
HRMS (EI): calcd. for C28H26O3S2Si: 502.1093; found 502.1095.
(film): ν = 3483, 2951, 1726, 1639, 1485, 1435, 1266, 1206, 1144,
˜
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1086, 922, 961, 912, 732 cm–1. H NMR (400 MHz): δ = 7.94 (m,
1 H), 7.46 (m, 1 H), 7.34 (m, 2 H), 5.60 (s, 1 H), 3.86, 3.84 (each
s, 3 H), 3.69 (m, 4 H), 2.79 (br. s, 1 H) ppm. 13C NMR (100 MHz):
δ = 167.1 (o), 165.7 (o), 147.5 (o), 139.6 (o), 133.7 (o), 129.6 (o),
128.8 (+), 128.4 (+, 2 C), 128.1 (+), 64.6 (+), 63.6 (o), 52.8 (+),
52.4 (+), 43.9 (–), 42.8 (–) ppm. MS (EI): m/z = 352, 320, 292, 260,
233, 145, 59. HRMS (EI): calcd. for C16H16O5S2: 352.0440; found
352.0439.
4Ј-Hydroxy-2ЈH-spiro[1,3-dithiolane-2,1Ј-naphthalene]-2Ј,2Ј,3Ј,3Ј
(4ЈH)-tetracarbonitrile (15b): Yield 162 mg (48%); m.p. 142–144 °C.
1Ј-{[Dimethyl(phenyl)silyl]oxy}-1ЈH,4ЈЈH-dispiro[1,3-dithiolane-
2,4Ј-isochromene-3Ј,1ЈЈ-naphthalen]-4ЈЈ-one (12b): Yield 187 mg
IR (KBr): ν = 3280, 2917, 2849, 1707, 1483, 1455, 1422, 1374, 1316,
˜
(38%); m.p. 145–146 °C. IR (film): ν = 2917, 1673, 1597, 1429,
˜
1246, 1207, 1144, 1045, 980, 893, 770, 744, 730 cm–1. 1H NMR
(200 MHz): δ = 7.93 (d, J = 7.6 Hz, 1 H), 7.61 (dt, J = 1.5, 7.4 Hz,
1 H), 7.43 (dt, J = 7.6, 1.5 Hz, 1 H), 7.21 (d, J = 7.4 Hz, 1 H), 5.31
(s, 1 H), 3.84 (m, 4 H) ppm. 13C NMR (50 MHz): δ = 137.6 (o),
137.5 (o), 132.8 (+), 132.5 (+), 129.8 (+), 127.5 (+), 110.4 (o), 110.3
(o), 108.7 (o), 108.6 (o), 80.5 (o), 80.1 (o), 60.4 (o), 53.5 (+), 43.8
(–), 43.2 (–) ppm. MS (EI): m/z = 338, 310, 267, 235, 209, 181, 164,
149, 121. HRMS (EI): calcd. for C16H10N4OS2: 338.0296; found
338.0297.
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1387, 1347, 1254, 1211, 1118, 1020, 957, 834, 699 cm–1. H NMR
(400 MHz): δ = 8.32 (dd, J = 0.9, 7.9 Hz, 1 H), 8.10 (dd, J = 1.0,
7.7 Hz, 1 H), 7.91 (m, 1 H), 7.60 (m, 3 H), 7.49 (dt, J = 1.0, 7.7 Hz,
1 H), 7.38 (d, J = 10.6 Hz, 1 H), 7.37 (m, 4 H), 7.28 (m, 2 H), 6.42
(s, 1 H), 6.25 (d, J = 10.6 Hz, 1 H), 3.21 (m, 1 H), 2.93 (m, 1 H),
2.67 (m, 1 H), 1.48 (m, 1 H), 0.51, 0.50 (each s, 3 H) ppm. 13C
NMR (100 MHz): δ = 184.7 (o), 146.8 (+), 140.3 (o), 137.6 (o),
136.7 (o), 133.7 (+), 133.6 (o), 133.3 (o), 130.3 (+), 129.8 (+), 129.0
(+), 129.0 (+), 128.8 (+), 128.0 (+), 127.9 (+), 127.7 (+), 126.6 (+),
124.6 (+), 91.4 (+), 77.1 (o), 76.8 (o), 41.9 (–), 40.9 (–), –1.3 (+),
–1.4 (+) ppm. MS (ESI): m/z = 525 [M + Na]+. HRMS (EI): calcd.
for C28H26O3S2Si: 502.1093; found 502.1094.
Dimethyl (2ЈS*,3ЈR*)-4Ј-Hydroxy-3Ј,4Ј-dihydro-2ЈH-spiro[1,3-di-
thiolane-2,1Ј-naphthalene]-2Ј,3Ј-dicarboxylate (17a): Yield 242 mg
(68%); m.p. 126–128 °C. IR (KBr): ν = 3466, 2954, 1784, 1741,
˜
4Ј-{[Dimethyl(phenyl)silyl]oxy}-2ЈH-spiro[1,3-dithiolane-2,1Ј-naph- 1484, 1437, 1364, 1286, 1200, 1059, 960, 855, 771, 683 cm–1. 1H
thalene]-2Ј,2Ј,3Ј,3Ј(4H)-tetracarbonitrile (15a): Yield 297 mg (63%). NMR (200 MHz): δ = 7.92 (d, J = 7.6 Hz, 1 H), 7.32 (m, 3 H),
IR (film): ν = 3072, 2961, 2273, 1774, 1481, 1428, 1259, 1209, 1117,
5.06 (d, J = 3.8 Hz, 1 H), 3.89 (d, J = 10.7 Hz, 1 H), 3.77, 3.76
(each s, 3 H), 3.61 (dd, J = 10.7, 3.8 Hz, 1 H), 3.48 (m, 4 H) ppm.
13C NMR (50 MHz): δ = 172.1 (o), 171.9 (o), 140.2 (o), 134.9 (o),
130.3 (+), 129.1 (+), 128.4 (+), 128.3 (+), 68.6 (o), 67.5 (+), 52.3
(+), 52.1 (+), 50.5 (+), 49.2 (+), 42.1 (–), 41.7 (–) ppm. MS (EI):
m/z = 354, 322, 294, 276, 262, 250, 234, 217, 202, 186, 149, 115,
˜
1
911, 826, 738 cm–1. H NMR (400 MHz): δ = 7.70 (d, J = 8.0 Hz,
1 H), 7.67 (m, 2 H), 7.46 (m, 4 H), 7.30 (m, 1 H), 7.13 (d, J =
8.0 Hz, 1 H), 5.49 (s, 1 H), 3.81 (m, 4 H), 0.74 (s, 3 H), 0.67 (s, 3
H) ppm. 13C NMR (100 MHz): δ = 134.1 (o), 133.9 (o), 133.8 (+,
2 C), 131.1 (+), 130.9 (+), 130.8 (o), 130.2 (+), 129.9 (+), 128.4 (+,
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Eur. J. Org. Chem. 2009, 1016–1021