S. Caddick et al. / Tetrahedron 56 (2000) 465–473
471
then reduced in vacuo and the residue purified by flash
chromatography (silica gel) [eluant—petrol/dichloro-
methane/ethyl acetate (gradient) 18:1:1, 8:1:1, 14:3:3] to
give the title compound (1.209 g, 63%) as a white crystall-
ine solid. Mp 110ЊC; nmax/cmϪ1: 3309 (CC–H) 1319 and
1154 (SO2); dH: 2.16–2.17 (t, J2.4 Hz, 1H, CCH) 2.56 (s,
3H, Ar–CH3) 2.59 (m, 2H, N–CH2CH2) 4.59–4.64 (t,
J7.9 Hz, 2H, N–CH2CH2) 7.30–7.4 (m, 1H, H5) 7.45
and 7.98 (AA0BB0, 4H, SO2Ar–H) 7.46–7.52 (m, 2H, H3
and H6) 7.82–7.85 (d, 1H, H7) 7.88–7.91 (m, 1H, H4); dC:
20.29, 22.09, 24.05, 43.77, 71.31, 111.00, 111.74, 121.87,
123.40, 125.79, 126.27, 128.15, 130.51, 135.10, 138.46,
139.07, 145.17.; HRMS (EI) C19H17NO2S requires
323.0980. Found 323.0980.
1-ynyl)-2-(toluene-4-sulfonyl)-1H-indole (0.100 g, 296 mmol),
Se-phenyl-p-tolueneselenosulfonate (0.101 g, 325 mmol) and
AIBN (0.013 g, 78 mmol) in benzene (12 ml) was stirred
under reflux for 4 h. The solution was allowed to cool to
room temperature, reduced in vacuo and the residue purified
by flash chromatography (silica gel) [eluant—petrol/dichloro-
methane/ethyl acetate (gradient) 18:1:1, 8:1:1, 4:1:1] to give
the title compound (0.065 g, 34%) as a white crystalline
solid. Mp 86ЊC; nmax/cmϪ1: 1318 and 1120 (SO2); dH:
1.91 (m 2H, N–CH2CH2CH2) 2.40 (s, 3H, Ar–CH3) 2.41
(s, 3H, Ar–CH3) 2.85 (m, 2H, N–CH2CH2CH2) 4.36 (t,
J7.9 Hz, 2H, N–CH2CH2CH2) 5.84 (s, 1H, C(Ts)H)
7.24–7.92 (m, 18H, Ar–H); dC: 22.07, 22.13, 30.44,
30.58, 44.40, 111.30, 111.36, 121.66, 123.31, 124.66,
125.81, 125.95, 126.23, 127.36, 128.21, 129.90, 130.38,
130.55, 130.62, 135.18, 137.09, 138.70, 139.17, 139.51,
144.58, 145.01, 159.43; HRMS (EI) C33H31NO4S2Se
requires 649.0860. Found 649.0900.
1-Pent-4-ynyl-2-(toluene-4-sulfonyl)-1H-indole 8. To a solu-
tion of 2-(toluene-4-sulfonyl)-1H-indole (0.402 g, 1.5 mmol),
triphenylphosphine (0.598 g, 2.3 mmol) and pent-4-yn-1-ol
(0.20 ml, 0.181 g, 2.2 mmol) in dichloromethane (25 ml) at
0ЊC was added dropwise diethyl azodicarboxylate (0.35 ml,
0.387 g, 2.2 mmol). The solution was allowed to warm to
room temperature overnight. The solution was reduced in
vacuo and the residue purified by flash chromatography (silica
gel) [eluant—petrol/dichloromethane/ethyl acetate (gradient)
18:1:1, 8:1:1, 14:3:3] to give the title compound (0.433 g,
87%) as a white crystalline solid. Mp 96ЊC (Lit.16 93–95ЊC);
nmax/cmϪ1: 3285 (CC–H) 1350 and 1152 (SO2); dH: 1.71–
1.79 (quint., J7.3 Hz, 2H, CH2CH2CH2) 1.99–2.12 (t,
J2.6 Hz, 1H, CCH) 2.12–2.18 (td, J6.8 Hz, J02.6 Hz,
2H, CH2CCH) 2.34 (s, 3H, Ar–CH3) 4.3–4.35 (dd,
J8.7 Hz, J07.1 Hz, 2H, N–CH2CH2) 7.08–7.14 (m, 1H,
H5) 7.23 (s, 1H, H3) 7.23 and 7.77 (AA0BB0, 4H, SO2Ar–H)
7.25–7.35 (m, 2H, H6 and H7) 7.62–7.63 (d, 1H, H4);
dC: 15.69, 21.28, 28.03, 43.37, 69.16, 82.57, 110.21,
110.66, 120.85, 122.54, 124.94, 125.36, 127.38,
129.60, 134.40, 137.85, 138.46, 144.24; HRMS (EI)
C20H19NO2S requires 337.1137. Found 337.1137.
1-[5-Phenylselanyl-6-(toluene-4-sulfonyl)-hex-5-enyl]-2-
(toluene-4-sulfonyl)-1H-indole 11. A solution of 1-hex-5-
ynyl-2-(toluene-4-sulfonyl)-1H-indole, (0.104 g, 296 mmol),
Se-phenyl-p-tolueneselenosulfonate (0.101 g, 325 mmol)
and AIBN (0.013 g, 78 mmol) in benzene (12 ml) was
stirred under reflux for 4 h. The solution was allowed to
cool to room temperature, reduced in vacuo and the residue
purified by flash chromatography (silica gel) [eluant—
petrol/dichloromethane/ethyl acetate (gradient) 18:1:1,
8:1:1, 4:1:1] to give the title compound (0.178 g, 91%) as
a white crystalline solid. Mp 89ЊC; nmax/cmϪ1: 1348 and
1151 (SO2); dH: 1.61–1.69 (m, 4H, CH2CH2) 2.44 (s, 3H,
Ar–CH2) 2.46 (s, 3H, Ar–CH3) 2.83–2.88 (t, J7.2 Hz, 2H,
CH2C(SePh)) 4.30–4.35 (t, J7.9 Hz, 2H, N–CH2CH2)
5.91 (s, 1H, C(Ts)H) 7.24–7.92 (m, 18H, Ar–H); dC:
22.03, 22.09, 27.69, 29.73, 32.87, 44.86, 111.15,
111.23, 121.56, 123.35, 124.57, 125.80, 126.06, 127.30,
128.13, 130.25, 130.48, 130.58, 135.21, 137.05, 138.77,
139.09, 139.70, 144.45, 145.01, 160.62; HRMS (EI)
C34H33NO4S2Se requires 663.1016. Found 663.1016.
1-Hex-5-ynyl-2-(toluene-4-sulfonyl)-1H-indole 9. To a
solution of 2-(toluene-4-sulfonyl)-1H-indole (0.415 g, 1.5
mmol), triphenylphosphine (0.597 g, 2.3 mmol) and hex-
5-yn-1-ol (0.25 ml, 0.223 g, 2.3 mmol) in dichloromethane
(25 ml) at 0ЊC was added dropwise diethyl azodicarboxylate
(0.35 ml, 0.387 g, 2.2 mmol). The solution was allowed to
warm to room temperature overnight. The solution was
reduced in vacuo and the residue purified by flash chromato-
graphy (silica gel) [eluant—petrol/dichloromethane/ethyl
acetate (gradient) 18:1:1, 8:1:1, 14:3:3] to give the title
compound (0.464 g, 87%) as a white crystalline solid. Mp
104ЊC; nmax/cmϪ1: 3295 (CC–H) 1347 and 1153 (SO2); dH:
1.41–1.46 (m, 2H, N–CH2CH2CH2) 1.58–1.6 (m, 2H, N–
CH2CH2CH2) 1.86–1.88 (t, J2.5 Hz, 1H, CCH) 2.04–2.1
(td, J6.9 Hz, J02.5 Hz, 2H, CH2CCH) 2.34 (s, 3H, Ar–
CH3) 4.2–4.23 (t, J7.8 Hz, 2H, N–CH2CH2CH2) 7.1–7.18
(m, 1H, H5) 7.22 (s, 1H, H3) 7.23 and 7.76 (AA0BB0, 4H,
SO2Ar–H) 7.24–7.28 (m, 2H, H6 and H7) 7.61–7.63 (m,
1H, H4); dC: 17.64, 21.28, 25.18, 28.58, 43.94, 68.41, 83.22,
110.24, 110.47, 120.66, 122.48, 124.90, 125.16, 127.24,
129.48, 134.25, 137.92, 138.25, 144.06; HRMS (EI)
C21H21NO2S requires 351.1293. Found 351.1293.
1-(Toluene-4-sulfonylmethylene)-2,3-dihydro-1H-3a-aza-
cyclopenta[a]indene 12. To a solution of 1-but-3-ynyl-2-
(toluene-4-sulfonyl)-1H-indole, (0.385 g, 1.2 mmol) in
benzene (50 ml) under reflux was added, via syringe pump
[flow rate1.78 ml h], a solution of Se-phenyl-p-toluenese-
lenosulfonate (0.093 g, 298 mmol) and AIBN (0.198 g,
1.2 mmol) in benzene (5 ml). Once the addition was
complete, the mixture was stirred under reflux for another
6 h. The solution was allowed to cool to room temperature,
reduced in vacuo and the residue purified by flash chroma-
tography (silica gel) [eluant—petrol/dichloromethane/ethyl
acetate (gradient) 18:1:1, 8:1:1, 4:1:1] to give the title
compound (0.342 g, 89%) as a white crystalline solid. Mp
195ЊC; nmax/cmϪ1: 2255, 1623 (CyC), 1345 and 1146
(SO2); dH: 2.49 (s, 3H, Ar–CH3) 3.85–3.89 (m, 2H,
N–CH2CH2) 4.24–4.29 (t, J6.4 Hz, 2H, N–CH2CH2)
6.68 (s, 1H, CyCHTs) 6.74 (s, 1H, H3) 7.14–7.19 (m, 1H,
H5) 7.24–7.34 (m, 2H, H6 and H7) 7.41 and 7.91 (AA0BB0,
4H, SO2Ar–H) 7.67–7.9 (m, 1H, H4); dC: 20.52, 31.68,
41.42, 94.53, 109.13, 117.34, 119.70, 121.21, 122.36,
126.06, 128.81, 131.55, 133.10, 138.07, 138.59, 143.14,
144.32; HRMS (EI); C19H17NO2S requires 323.0980.
Found 323.0980.
1-[4-Phenylselanyl-5-(toluene-4-sulfonyl)-pent-4-enyl]-
2-(toluene-4-sulfonyl)-1H-indole 10. A solution of 1-(pent-