V. Maraval, C. Duhayon, Y. Coppel, R. Chauvin
C– and O–Si(CH3)3], 5.30 and 5.69 (2 s, 2 H, O–CH), 7.30–7.63 NMR (CDCl3): δ = 42.99 (s, C-3), 49.83 (s, C-2), 124.19 (s, C-8),
FULL PAPER
(m, 10 H, o-, m-, p-CH) ppm. 13C{1H} NMR (CDCl3): δ = 0.00
and 0.06 [2 s, C– and O–Si(CH3)3], 69.39 and 70.26 (2 s, O–CH),
92.82 and 93.11 (2 s, O-C-Cϵ), 102.90 and 103.03 (2 s, ϵC–SiMe3),
127.89 and 128.12 (2 s, o-C), 128.41 (s, p-C), 128.55 and 128.62 (2
s, m-C), 138.08 and 138.19 (2 s, i-C) ppm. MS (DCI/NH3): m/z =
391.4 [M + H]+, 408.4 [M + NH4]+, 425.4 [M + N2H7]+.
125.58 (s, p-C), 126.70 (s, C-6), 126.87 (s, Co), 127.69 (s, C-5),
128.44 (s, m-C), 134.26 (s, C-7), 136.59 (s, C-4), 144.59 (s, i-C),
159.11 (s, C-9), 205.57 (s, C-1) ppm. MS (DCI/NH3): m/z = 280.3
[M]+, 281.3 [M + H]+, 298.3 [M + NH4]+, 315.3 [M + N2H7]+.
1,1Ј-Diphenyl-1,1Ј-dipropynyl Ether (7a): Potassium carbonate
(0.425 g, 3.07 mmol) was added to a solution of 7b (0.120 g,
0.31 mmol) in methanol (10 mL), and the resulting mixture was
stirred for 2 h at room temperature. The mixture was filtered, and
the resulting solution was concentrated under reduced pressure and
was then diluted with Et2O. After treatment with saturated aqueous
NH4Cl and extraction with Et2O, the organic layers were com-
bined, washed with brine, and dried with MgSO4, and the solvents
were evaporated to dryness, thus giving 7a as a orange, viscous oil
1,1,6,6-Tetraphenyl-3,4-bis(trimethylsilyl)hex-1,2,4,5-tetraene (10):
Silica gel chromatography (elution with diethyl ether/pentane, 1:99)
afforded crude crystals of 10 (m.p. 122 °C). Yields: Procedure C,
62%.1H NMR (CDCl3): δ = 0.13 [s, 18 H, (CH3)3Si], 7.29–7.40 (m,
20 H, ar-H) ppm. 13C{1H} NMR (CDCl3): δ = –0.65 [s, Si(CH3)3],
98.17 [s, =C–Si(CH3)3], 105.88 (s, Ph–C=), 126.67 (s, p-C), 128.19
(s, o-C), 128.39 (s, m-C), 136.89 (s, i-C), 208.36 (s, C=C=C) ppm.
MS (DCI/NH3): m/z = 527.5 [M + H]+, 544.5 [M + NH4]+.
1
(0.075 g, quantitative). H NMR (CDCl3): δ = 2.70 and 2.75 (2 d,
4J = 2.2 Hz, 1 H each, ϵCH), 5.30 and 5.71 (2 d, 4J = 2.2 Hz, 1
H each, O–CH), 7.35–7.38 (m, 2 H, p-CH), 7.38–7.44 (m, 4 H, m-
3
4
CH), 7.55–7.57 and 7.61–7.63 (2 dd, J = 7.7, J = 1.1 Hz, 4 H, o-
CH) ppm. 13C{1H} NMR (CDCl3): δ = 68.92 and 69.43 (2 s, O–
C), 75.98 and 76.32 (2 s, ϵC–H), 81.08 and 81.48 (2 s, C–Cϵ),
127.60 and 127.81 (2 s, o-C), 128.51 and 128.69 (2 s, m-C), 128.58
and 128.87 (2 s, p-C), 137.55 and 137.78 (2 s, i-C) ppm. MS (DCI/
NH3): m/z = 264.2 [M + NH4]+, 281.2 [M + N2H7]+.
Indenylallene (11): Silica gel chromatography (elution with diethyl
ether/pentane, 1:99) afforded 11 as crude crystals (m.p. 136 °C).
Yields: Procedure B, 50%; Procedure E, 67%. 1H NMR (CDCl3): δ
= –0.08 [s, 9 H, C-8–Si(CH3)3], 0.18 [s, 9 H, C-10–Si(CH3)3], 6.75–
6.78 (dd, 3J = 8.1, 4J = 1.5 Hz, 2 H, o-CH–C-12), 7.11–7.49 (m, 17
H, ar-CH) ppm. 13C{1H} NMR (CDCl3): δ = –2.98 [s, C-8–Si(CH3)
3], 0.60 [s, C-10–Si(CH3)3], 67.83 (s, C-8), 98.35 (s, C-10), 104.53 (s,
C-12), 120.11 (s, C-3), 123.87 (s, C-6), 124.72 (s, C-4), 126.14 (s, p-
C), 127.03 (s, p-C), 127.10 (s, C-5), 127.67 (s, o-C or m-C), 127.77
(s, p-C), 128.19 (s, o-C or m-C), 128.32 (s, o-C or m-C), 128.66 (s,
o-C or m-C), 129.58 (s, o-C or m-C), 129.90 (s, o-C or m-C), 135.23
(s, i-C–C-1), 136.15 (s, i-C–C-12), 136.82 (s, i-C–C-12), 138.85 (s,
C-9), 142.76 (s, C-2 or C-7), 142.85 (s, C-7 or C-2), 146.68 (s, C-
1), 206.29 (s, C-11) ppm. MS (DCI/NH3): m/z = 527.4 [M – Cl +
H]+, 544.4 [M – Cl + NH4]+.
1,1Ј-Diphenyl-1,1Ј-dibutynyl Ether (7c): Silica gel chromatography
(elution with diethyl ether/pentane, 5:95) allowed for the separation
of the two diastereoisomers of 7c as orange oils. Yields: Pro-
cedure C, 60%; Procedure D, 94%; Procedure E, 50%. Diastereoiso-
mer I: 1H NMR (CDCl3): δ = 1.93 (d, 5J = 2.1 Hz, 6 H, CH3), 5.22
(q, 5J = 2.1 Hz, 2 H, CH–O), 7.29–7.54 (m, 10 H, o-, m-, p-
CH) ppm. 13C{1H} NMR (CDCl3): δ = 3.93 (s, CH3), 69.11 (s, O–
C), 77.34 (s, ϵC–CH3), 84.03 (s, O-C-Cϵ), 127.80 (s, o-C), 128.40
(s, p-C), 128.49 (s, m-C), 138.90 (s, i-C) ppm. Diastereoisomer II:
5
1H NMR (CDCl3): δ = 1.98 (d, J = 2.1 Hz, 6 H, CH3), 5.62 (q,
Fused Tetracycle 12: Silica gel chromatography (elution with diethyl
ether/pentane, 5:95) gave a mixture from which 12 precipitated as
white crystals from dichloromethane (m.p. 217 °C). Yield: Pro-
5J = 2.1 Hz, 2 H, CH–O), 7.34–7.63 (m, 10 H, o-, m-, p-CH) ppm.
13C{1H} NMR (CDCl3): δ = 3.88 (s, CH3), 69.44 (s, O–C), 77.05
(s, ϵC–CH3), 84.12 (s, O-C-Cϵ), 127.54 (s, o-C), 128.12 (s, p-C),
128.35 (s, m-C), 139.33 (s, i-C) ppm. MS (DCI/NH3): m/z = 275.2
[M + H]+, 292.3 [M + NH4]+, 309.3 [M + N2H7]+.
1
cedure E, 23%. H NMR (CDCl3): δ = 1.68 (s, 3 H, 1-H3), 1.72 (s,
3 H, 18-H3), 2.70, 3.48 (2 d, 2J = 16.8 Hz, 2H, 5-H2), 5.80–7.70
(m, 29 H, ar-CH) ppm. 13C{1H} NMR (CDCl3): δ = 22.33 (s, C-
1), 26.76 (s, C-18), 35.59 (s, C-5), 51.22 (s, C-6), 58.15 (s, C-15),
68.01 (s, C-17), 115.46 (s, C-2), 120.74 (s, C-11), 120.91 (s, C-8),
124.95 (s, CPh), 125.49 (s, C-9), 125.51 (s, CPh), 126.04 (s, CPh),
126.24 (s, CPh), 126.56 (s, CPh), 126.75 (s, CPh), 126.84 (s, C-10),
126.88 (s, CPh), 127.23 (s, CPh), 127.40 (s, CPh), 127.50 (s, CPh),
128.56 (s, CPh), 128.59 (s, CPh), 128.92 (s, CPh), 129.51 (s, CPh),
130.52 (s, CPh), 135.53 (s, CPh), 138.27 (s, CPh), 138.90 (s, CPh),
141.46 (s, CPh), 141.60 (s, C-13), 141.63 (s, CPh), 141.99 (s, C-3),
144.84 (s, C-12), 146.60 (s, C-4 or C-16), 151.68 (s, C-7), 151.81 (s,
C-14), 156.84 (s, C-4 or C-16) ppm. MS (DCI/CH4): m/z = 571.21
[M – C6H5]+, 613.28 [M – Cl]+, 649.26 [M]+.
1,1,4,4-Tetraphenyl-3,6-bis(trimethylsilyl)hex-1,2-dien-5-yne (8): Sil-
ica gel chromatography (elution with diethyl ether/pentane, 2:98)
afforded 8 as pale yellow–brown crystals (m.p. 86 °C). Yields: Pro-
cedure A, 25%; Procedure A from 5b-TMS, 18%; Procedure C from
5b-[Co] and a 15 h reaction time, 51%. 1H NMR (CDCl3): δ = 0.14
[s, 9 H, (CH3)3Si–C=], 0.28 [s, 9 H, (CH3)3Si–Cϵ], 7.03–7.46 (m,
20 H, ar-H) ppm. 13C{1H} NMR (CDCl3): δ = 0.01 and 0.62 [2 s,
(CH3)3Si–C-1 and (CH3)3Si–C-4], 54.78 (s, C-3), 90.80 (s, C-2),
108.54, 109.36, 110.00 (3 s, C-1, C-4 and C-6), 126.56 and 126.65
(2 s, p-C), 127.70, 127.93, 128.19, 128.40 (4 s, o-C and p-C), 136.77
and 143.93 (2 s, i-C), 207.84 (s, C-5) ppm. MS (DCI/NH3): m/z =
544.4 [M + NH4]+.
Fused Pentacycle 13: Silica gel chromatography (elution with di-
ethyl ether/pentane, 5:95) afforded a mixture, from which 13 pre-
cipitated as white crystals from diethyl ether (m.p. 206 °C). Yield:
Procedure E, 13%. 1H NMR (CDCl3): δ = 1.22 (s, 3 H, 20-H3),
3–Phenyl-3-trimethylsilylindan-1-one (9): Silica gel chromatography
(elution with diethyl ether/pentane, 2:98) gave 9 as an orange oil.
Yields: Procedure A, 50%; Procedure A at room temperature for 24
1
h, 62%; Procedure A from 5b-TMS, 51%. H NMR (CDCl3): δ =
2.68 (d, 2J = 15.9 Hz, 1 H, 18-H2), 2.74 (dd, 2J = 15.9, 4J = 2.0 Hz,
1
1
4
0.0 [s, 9 H, (CH3)3Si], 3.03 (d, J = 19.6 Hz, 1 H, 2-H), 3.27 (d, J 1 H, 18-H2), 3.29 (s, 1 H, 19-H), 6.05 (d, J = 2.0 Hz, 1 H, 2-H),
3
4
= 19.6 Hz, 1 H, 2-H), 7.20 (tt, J = 7.2, J = 1.2 Hz, 1 H, p-CH), 6.97–7.34 (m, 18 H, ar-CH) ppm. 13C{1H} NMR (CDCl3): δ =
7.32 (dd, 3J = 8.3 Hz, 2 H, m-CH), 7.37 (dd, J = 7.2, J = 1.2 Hz,
30.72 (s, C-20), 42.99 (s, C-18), 49.73 (s, C-17), 59.60 (s, C-3), 68.82
3
4
3
4
2 H, o-CH), 7.42 (ddd, J = 6.1, J = 2.0 Hz, 1 H, 6-H), 7.70 (dd, (s, C-10), 75.96 (s, C-19), 121.86 (s, C-15), 124.64 (s, C-8), 124.98
3J = 6.1, J = 2.0 Hz, 1 H, 5-H), 7.70 (ddd, J = 6.1, J = 2.0 Hz,
(s, C-5), 125.64 (s, C-12), 126.19 (s, C-30), 126.35 (s, C-24), 127.23
(s, C-22 and C-26), 127.61 (s, C-13), 127.95 (s, C-14, C-29 and C-
4
3
4
1 H, 7-H), 7.83 (dd, 3J = 6.1, 4J = 2.0 Hz, 1 H, 8-H) ppm. 13C{1H}
5154
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Eur. J. Org. Chem. 2008, 5144–5156