S. Sumi et al. / Tetrahedron 59 (2003) 8571–8587
8585
(m, 4H), 7.24 (m, 6H), 7.11 (d, 1H, J¼8.5 Hz), 6.74 (d, 1H,
J¼8.5 Hz), 6.50 (d, 1H, J¼13.0 Hz), 6.10 (d, 1H,
J¼13.0 Hz), 4.64 (s, 1H), 3.90 (s, 3H), 3.80 (q, 2H,
J¼7.1 Hz), 3.76 (m, 4H), 3.55 (s, 3H), 3.34 (s, 3H), 3.26 (s,
3H), 2.95–3.10 (m, 1H), 2.80 (d, 1H, J¼15.0 Hz), 2.67 (d,
1H, J¼15.0 Hz), 1.95 (m, 4H), 1.52 (s, 9H), 1.17 (s, 9H),
0.83 (t, 3H, J¼7.1 Hz); 13C NMR (100 MHz, C6D6, 608C) d
171.6, 150.4, 138.4, 136.0, 134.8, 133.5, 130.4, 129.7,
128.5, 128.1, 127.9, 127.0, 120.1, 114.1, 111.3, 111.2, 83.2,
65.4, 62.4, 60.4, 59.8, 58.3, 58.2, 57.5, 49.7, 31.6, 29.5,
28.4, 27.4, 19.7, 14.2; HR-MS (FAB) calcd for
C46H63NO10Si [Mþ] 817.4221, found 817.4218.
7.73 (d, 1H, J¼7.8 Hz), 7.08 (d, 1H, J¼7.8 Hz), 6.91 (d, 1H,
J¼7.8 Hz), 6.72 (t, 1H, J¼7.8 Hz), 6.66 (t, 1H, J¼7.8 Hz),
6.61 (d, 1H, J¼7.8 Hz), 6.38 (d, 1H, J¼12.7 Hz), 6.02 (d,
1H, J¼12.7 Hz), 4.50 (s, 1H), 3.90 (s, 3H), 3.50 (s, 3H),
3.32 (m, 3H), 3.28 (s, 3H), 3.22 (s, 3H), 2.95 (m, 1H), 2.61
(d, 1H, J¼15.6 Hz), 2.53 (d, 1H, J¼15.6 Hz), 1.82–1.61
(m, 4H), 1.55 (s, 9H), 0.86 (t, 3H, J¼6.8 Hz); 13C NMR
(100 MHz, C6D6, 60 8C) d 171.8, 150.9, 150.7, 148.4, 141.2,
138.2, 134.7, 134.0, 132.8, 132.0, 130.7, 130.4, 128.1,
126.1, 125.2, 119.7, 113.7, 111.5, 111.2, 83.9, 63.6, 60.5,
60.1, 58.42, 58.41, 57.4, 49.7, 43.7, 31.3, 28.5, 28.1, 26.1,
14.3; HR-MS (FAB) calcd for C36H49NO13S [Mþ]
763.2986, found 763.2978.
4.1.40. (1Z)-(3R)-2-[6-(tert-Butyl-diphenyl-silanyloxy)-3-
dimethoxymethyl-3-ethoxycarbonylmethyl-hex-1-enyl]-
6,7-dimethoxy-3-[2-(2-nitro-benzenesulfonylamino)-
ethyl]-indole-1-carboxylic acid tert-butyl ester (34). To a
solution of the 3-indolylethanol derivative (2.21 g,
2.71 mmol) in benzene (60 mL) were added PPh3 (0.99 g,
4.1.42. (11R)-(12Z)-11-Dimethoxymethyl-11-ethoxycar-
bonylmethyl-1,2-dimethoxy-7-(2-nitrobenzenesulfonyl)-
6,7,8,9,10,11-hexahydro-5H-7,14-diaza-cycloundeca-
[a]indene-14-carboxylic acid tert-butyl ester (33). To a
solution of the above alcohol (1.72 g, 2.25 mmol) in
benzene (60 mL) were added PPh3 (0.76 g, 2.91 mmol),
and DEAD (40% solution in toluene, 1.32 mL, 2.91 mmol)
at room temperature under Ar. After being stirred for 5 min,
the reaction mixture was evaporated under reduced
pressure. The residue was slurried in EtOAc–hexane (1:1)
to precipitate triphenylphosphine oxide, filtered, and
evaporated under reduced pressure. Flash column chroma-
tography on silica gel (CHCl3–MeOH, 150:1) afforded 33
(0.55 g, 92.4%) as yellow foam; [a]2D5¼þ14.3 (c 0.33,
CHCl3); IR (film, cm21) 2981, 2939, 2834, 1732, 1544,
3.79 mmol),
2-nitrobenzenesulfonamide
(o-NsNH2)
(0.77 g, 3.79 mmol), and DEAD (40% solution in toluene,
1.71 mL, 3.79 mmol) at room temperature under Ar. After
being stirred for 5 min, the reaction mixture was cooled in
an ice bath to precipitate triphenylphosphine oxide, filtered,
and evaporated under reduced pressure. Flash column
chromatography on silica gel (CH2Cl2–hexane, 3:1)
afforded 34 (2.51 g, 92.7%) as yellow oil; [a]2D5¼21.9 (c
0.31, CHCl3); IR (film, cm21) 3322, 2935, 2900, 2859,
1732, 1541, 1501, 1428, 1367, 1258, 1170, 1111; 1H NMR
(400 MHz, C6D6, 608C) d 7.77 (dt, 4H, J¼7.3, 2.2, 2.2 Hz),
7.69 (d, 1H, J¼8.5 Hz), 7.25 (m, 6H), 7.08 (d, 1H,
J¼8.5 Hz), 6.84 (d, 1H, J¼8.5 Hz), 6.68 (td, 1H, J¼7.6,
2.0 Hz), 6.63 (td, 1H, J¼7.6, 2.0 Hz), 6.57 (d, 1H, J¼
8.5 Hz), 6.38 (d, 1H, J¼12.9 Hz), 6.00 (d, 1H, J¼12.9 Hz),
5.24 (br s, 1H), 4.53 (s, 1H), 3.86 (s, 3H), 3.78 (m, 2H), 3.65
(br s, 2H), 3.50 (s, 3H), 3.32 (m, 3H), 3.29 (s, 3H), 3.24 (s,
3H), 3.16 (br s, 1H), 2.63 (d, 1H, J¼14.7 Hz), 2.52 (d, 1H,
J¼14.7 Hz), 1.85 (m, 4H), 1.54 (s, 9H), 1.16 (s, 9H), 0.82 (t,
3H, J¼7.1 Hz); 13C NMR (100 MHz, C6D6, 608C) d 171.4,
150.3, 148.0, 141.0, 138.0, 136.0, 134.7, 134.3, 133.9,
132.4, 131.7, 130.5, 130.1, 129.8, 128.4, 128.1, 127.9,
125.8, 125.0, 119.5, 113.4, 111.2, 110.9, 83.6, 65.3, 60.3,
59.9, 58.5, 58.1, 57.3, 49.6, 43.7, 28.2, 28.0, 27.4, 25.8,
19.7, 14.2; HR-MS (FAB) calcd for C52H67NO13SSi [Mþ]
1001.4164, found 1001.4169.
1
1503, 1371, 1348, 1257, 1153, 1073; H NMR (400 MHz,
C6D6, 608C) d 7.52 (d, 1H, J¼8.5 Hz), 7.21 (d, 1H,
J¼8.5 Hz), 6.78 (m, 2H), 6.76 (d, 1H, J¼8.5 Hz), 6.60 (br t,
1H, J¼7.8 Hz), 6.29 (d, 1H, J¼24.9 Hz), 6.26 (d, 1H,
J¼24.9 Hz), 4.63 (s, 1H), 3.96 (dd, 1H, J¼7.1, 2.4 Hz), 3.94
(dd, J¼7.1, 2.4 Hz), 3.91 (s, 3H), 3.78 (m, 2H), 3.51 (s, 3H),
3.28 (s, 3H), 3.11–3.24 (m, 2H), 2.95 (d, 1H, J¼16.0 Hz),
2.86 (dd, J¼12.0, 6.0 Hz), 2.60 (d, 1H, J¼16.0 Hz), 2.02
(m, 1H), 1.94 (m, 1H), 1.84 (m, 2H), 1.48 (s, 9H), 0.98 (t,
3H, J¼7.1 Hz); 13C NMR (100 MHz, C6D6, 608C) d 171.7,
151.1, 150.4, 149.1, 141.9, 138.0, 133.7, 133.3, 132.7,
131.3, 130.7, 127.8, 126.5, 123.8, 120.8, 115.2, 111.6,
111.1, 83.5, 60.6, 60.0, 58.5, 58.0, 57.3, 50.4, 49.3, 41.2,
32.3, 28.1, 27.6, 26.1, 14.5; HR-MS (FAB) calcd for
C36H47N3O12S [Mþ] 745.2880, found 745.2871.
4.1.43. (11R)-(12Z)-11-Ethoxycarbonylmethyl-11-for-
myl-1,2-dimethoxy-7-(2-nitro-benzenesulfonyl)-
6,7,8,9,10,11-hexahydro-5H-7,14-diazacycloundeca
[a]indene-14-carboxylic acid tert-butyl ester (35). To a
solution of 33 (1.46 g, 1.95 mmol) in CH2Cl2 (45 mL) was
added TMSBr (0.34 mL, 2.54 mmol) at -708C under Ar.
After being stirred for 15 min, the reaction mixture was
diluted with THF (15 mL), poured into the mixture of
phosphate buffer (0.2 M, pH 7.0, 45 mL) and THF (9 mL)
with vigorous stirring, and separated. The aqueous phase
was extracted with CH2Cl2 (15 mL). The combined organic
extracts were dried over MgSO4, filtered, and evaporated
under reduced pressure. Since compound 35 was regener-
ated during post-treatment, the residue was dissolved in
CH2Cl2 (45 mL), and TMSBr (0.15 mL, 1.17 mmol) was
added at 2708C under Ar. After being stirred for 15 min, the
same post-treatment was performed. The residue was
purified by flash column chromatography on silica gel
4.1.41. (1Z)-(3R)-2-(3-Dimethoxymethyl-3-ethoxycar-
bonylmethyl-6-hydroxy-hex-1-enyl)-6,7-dimethoxy-3-[2-
(2-nitro-benzenesulfonylamino)-ethyl]-indole-1-car-
boxylic acid tert-butyl ester. To a solution of the Ns-amide
34 (2.48 g, 2.47 mmol) in THF (50 mL) was added TBAF
(1 M solution in THF, 5.0 mL, 5.0 mmol) at room
temperature. After being stirred for an hour, the reaction
mixture was diluted with CH2Cl2 (30 mL) and washed with
brine (20 mL£2). The aqueous phase was extracted with
CH2Cl2 (10 mL). The combined organic extract were dried
over MgSO4, filtered, and evaporated under reduced
pressure. Flash column chromatography on silica gel
(EtOAc–hexane, 1:1–2:1 gradient) afforded the titled
alcohol derivative (1.76 g, 93.0%) as a yellow oil;
[a]D25¼210.8 (c 0.30, CHCl3); IR (film, cm21) 3568,
3316, 2980, 2938, 1732, 1542, 1501, 1444, 1368, 1344,
1258, 1164, 1089, 1072; 1H NMR (400 MHz, C6D6, 608C) d