T. Wandlowski, M. Mayor et al.
FULL PAPER
3
4
3JH,H = 7.0 Hz, 3 H, CH3), 1.31 [s, 9 H, C(CH3)3], 1.33 [s, 9 H,
H, OCH), 7.48 (dd, JH,H = 8.0, JH,H = 1.6 Hz, 2 H), 7.52 (dt,
3
3
4
C(CH3)3], 3.70 (q, JH,H = 7.1 Hz, 2 H, OCH2), 6.92 (d, JH,H
=
3JH,H = 7.9, JH,H = 1.5 Hz, 2 H), 7.54–7.57 (m, 4 H), 7.75 (d,
3
8.8 Hz, 1 H), 6.97(1) (s, 1 H, OCH), 6.97(3) (d, JH,H = 7.6 Hz, 1
4JH,H = 1.6 Hz, 2 H), 7.90 (t, 4JH,H = 1.4 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 14.7 (CH3), 31.2 (CH3), 47.0 (SC), 60.2
(OCH2), 88.5 (CϵC), 88.6 (CϵC), 89.5 (CϵC), 93.5 (CϵC), 93.7
3
4
3
H), 7.16 (dd, JH,H = 8.0, JH,H = 2.0 Hz, 1 H), 7.36 (t, JH,H
=
3
3
7.8 Hz, 1 H), 7.38 (t, JH,H = 8.2 Hz, 1 H), 7.48 (dd, JH,H = 8.0,
4JH,H = 1.6 Hz, 1 H), 7.50–7.60 (m, 5 H), 7.68 (d, JH,H = 2.4 Hz, (CϵC), 105.2, 119.9 (OCH), 123.2, 123.7, 124.9, 125.8, 125.9,
4
4
4
1 H), 7.74 (d, JH,H = 1.6 Hz, 1 H), 7.78 (t, JH,H = 1.4 Hz, 1 H),
128.7, 131.6, 131.8, 131.9, 133.9, 135.6, 137.0, 140.2, 147.3 (OC)
ppm. C51H40O3S2·0.5H2O (774.00): calcd. C 79.14, H 5.34; found
4
3
7.80 (t, JH,H = 1.6 Hz, 1 H), 7.83 (d, JH,H = 8.0 Hz, 1 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 11.4 (SiCH), 15.0 (CH3), 18.8 C 79.24, H 5.47. MS (EI): m/z (%) = 764.2 (100) [M]+, 708.0 (11)
(CH3), 31.1 (CH3), 31.2 (CH3), 46.6 (SC), 47.0 (SC), 59.8 (OCH2), [M – C4H9 + H]+, 652.2 (53) [M – 2 C4H9 + 2 H]+, 596.1 (5) [M –
88.3 (CϵC), 88.9 (CϵC), 89.3 (CϵC), 89.4 (CϵC), 91.8 (CϵC), 2 C4H9 – C3H6O + 4 H]+, 57.1 (29) [C4H9]+.
92.7 (CϵC), 93.3(6) (CϵC), 93.4 (CϵC), 98.0 (CϵC), 100.2
S,SЈ-[35,36-Dihydroxyhexacyclo[32.2.2.112,16.119,23.04,9.026,31]-
(CϵC), 102.2, 104.6, 105.5, 119.8 (OCH), 123.3, 123.4, 123.4(5),
tetraconta-1(36),4,6,8,12(40),13,15,19(39),20,22,26,28,30,34,37-pen-
123.5, 123.7, 124.7, 125.3, 125.8, 128.6, 128.8, 130.1, 131.7, 131.8,
131.9(7) (2 C), 132.0, 133.3, 133.8, 134.7, 135.0, 137.0, 138.4, 138.9,
140.3, 140.9, 147.1 (OC), 147.6 (OC) ppm. C60H61IO3S2Si
tadecaene-2,10,17,24,32-pentayne-7,28-diyl] Diethanethioate (1):
Boron tribromide (1 in CH2Cl2, 650 µL, 0.65 mmol) was added
in five equal portions over 4 h to a degassed solution of compound
(1049.24): calcd. C 68.68, H 5.86; found C 68.92, H 5.77. MS
6 (49 mg, 64.0 µmol) in a mixture of dry toluene (12 mL) and acetyl
chloride (3 mL). The resulting solution was stirred at room temp.
for 1 h. The solution was poured onto ice and the product was
extracted with CH2Cl2. The combined organic layers were dried
with MgSO4, filtered and the solvents evaporated to dryness. Flash
chromatography (SiO2, CH2Cl2/MeOH, 100:0 to 99:1) afforded 1
(28 mg, 64%) as a brown solid; m.p. Ͼ 370 °C. Rf = 0.26 (SiO2,
CH2Cl2/MeOH, 99:1). 1H NMR (400 MHz, CDCl3): δ = 2.47 (s, 6
(FAB): m/z (%) = 1048.3 (1) [M]+, 961.2 (1) [M – C4H9 – 2 CH3]+,
905.1 (1) [M – C4H9 – 2 C3H7]+, 849.1 (1) [M – C4H9 – 2 C3H7 –
C3H6O + 2 H]+, 57.0 (100) [C4H9]+.
4-{[4-(tert-Butylsulfanyl)-2-({3-[(3-{[5-(tert-butylsulfanyl)-2-
iodophenyl]ethynyl}phenyl)ethynyl]phenyl}ethynyl)phenyl]ethynyl}-2-
ethoxy-7-ethynyl-1,3-benzodioxole (13): TBAF (1 solution in
THF, 670 µL, 0.67 mmol) was added to a degassed solution of
compound 12 (117 mg, 0.11 mmol) in THF (10 mL) containing one
drop of glacial AcOH. The resulting solution was stirred at room
temp. for 20 min and the solvents were evaporated. Flash
chromatography (SiO2, hexane/CH2Cl2, 70:30) afforded 13 (95 mg,
95%) as a white solid; m.p. 81–82 °C. Rf = 0.30 (SiO2, hexane/
3
H, CH3), 6.43 (s, 2 H, OH), 7.10 (s, 2 H), 7.35 (t, JH,H = 7.6 Hz,
3
4
3
2 H), 7.37 (dd, JH,H = 8.0, JH,H = 1.6 Hz, 2 H), 7.50 (dt, JH,H
4
3
4
= 7.9, JH,H = 1.3 Hz, 2 H), 7.52 (dt, JH,H = 7.6, JH,H = 1.4 Hz,
3
4
2 H), 7.60 (d, JH,H = 8.0 Hz, 2 H), 7.66 (d, JH,H = 1.6 Hz, 2 H),
8.09 (t, JH,H = 1.4 Hz, 2 H) ppm. 13C NMR (125 MHz, CDCl3):
4
1
3
CH2Cl2, 50:50). H NMR (400 MHz, CDCl3): δ = 1.23 (t, JH,H
=
δ = 30.5 (CH3), 88.2 (CϵC), 89.4 (CϵC), 89.5 (CϵC), 94.3 (CϵC),
95.7 (CϵC), 111.0, 123.0, 123.2, 123.6, 125.8, 126.2, 128.6, 128.8,
131.4, 131.8, 132.4, 134.0, 136.3, 137.9, 145.0 (C-OH), 193.1 (C=O)
ppm. C44H24O4S2·2.2H2O (720.42): calcd. C 73.36, H 3.97; found
C 73.43, H 4.03. MS (FAB): m/z (%) = 719.3 (1) [M + K]+, 681.2
(1) [M + H]+, 680.3 (1) [M]+, 38.9 (100).
7.2 Hz, 3 H, CH3), 1.31 [s, 9 H, C(CH3)3], 1.33 [s, 9 H, C(CH3)3],
3
3.36 (s, 1 H, ϵCH), 3.71 (q, JH,H = 7.1 Hz, 2 H, OCH2), 6.95 (d,
3JH,H = 8.4 Hz, 1 H), 7.01 (s, 1 H, OCH), 7.02 (d, JH,H = 8.8 Hz,
3
3
4
3
1 H), 7.16 (dd, JH,H = 8.0, JH,H = 2.0 Hz, 1 H), 7.36 (t, JH,H
=
3
3
7.6 Hz, 1 H), 7.38 (t, JH,H = 8.0 Hz, 1 H), 7.48 (dd, JH,H = 7.8,
4JH,H = 1.8 Hz, 1 H), 7.50–7.60 (m, 5 H), 7.68 (d, JH,H = 2.4 Hz,
4
4
4
1 H), 7.75 (d, JH,H = 1.2 Hz, 1 H), 7.78 (t, JH,H = 1.6 Hz, 1 H),
Crystal Data for 6: C51H40O3S2, M = 765.01, F(000) = 804, yellow
4
3
3
¯
7.79 (t, JH,H = 1.6 Hz, 1 H), 7.83 (d, JH,H = 8.0 Hz, 1 H) ppm.
plate, size 0.03ϫ0.13ϫ0.27 mm , triclinic, space group P1, Z = 2,
13C NMR (100 MHz, CDCl3): δ = 14.8 (CH3), 31.1 (CH3), 31.2
a = 10.3054(5) Å, b = 13.7858(8) Å, c = 14.4700(8) Å, α =
(CH3), 46.6 (SC), 47.0 (SC), 59.7 (OCH2), 77.4 (CϵC), 83.3 97.504(3)°, β = 98.777(3)°, γ = 97.825(3)°, V = 1988.54(19) Å3,
(CϵC), 88.3 (CϵC), 88.5 (CϵC), 89.2(8) (CϵC), 89.3 (CϵC), 91.8 Dcalcd. = 1.278 Mgm–3. The crystal was measured on a KappaA-
(CϵC), 92.7 (CϵC), 93.5 (CϵC), 93.6 (CϵC), 102.2, 103.8, 105.2, PEX diffractometer at 123 K by using graphite-monochromated
119.9 (OCH), 123.3, 123.4, 123.5, 123.6, 124.9, 125.3, 125.6, 125.8,
128.6, 128.8, 130.0, 131.7, 131.8, 131.8(5), 131.9, 132.0, 133.3, maximal transmission 0.98/0.99, µ = 0.178 mm–1. The Apex2 pro-
134.0, 134.7, 135.0, 137.0, 138.4, 138.9, 140.3, 140.8, 147.0 (OC),
gram package[51] has been used for data collection and integration.
147.8 (OC) ppm. C51H41IO3S2 (892.90): calcd. C 68.60, H 4.63; From a total of 85370 reflections, 11615 were independent (merging
Mo-Kα radiation with λ = 0.71073 Å, Θmax = 30.033°. Minimal/
found C 68.85, H 4.79. MS (FAB): m/z (%) = 892.2 (4) [M]+, 791.2
(1) [M – C4H9 – C2H5O + H]+, 735.1 (1) [M – 2 C4H9 – C2H5O +
2 H]+, 706.1 (1) [M – 2 C4H9 – C3H6O2 + 2 H]+, 609.2 (1) [M – 2
C4H9 – C2H5O – I + 3 H]+, 57.0 (100) [C4H9]+.
r = 0.032). From these, 8429 were considered as observed
[IϾ2.0σ(I)] and were used to refine 568 parameters. The structure
was solved by direct methods using the program SIR92.[52] Least-
squares refinement against F was carried out on all non-hydrogen
atoms using the program CRYSTALS.[53] R = 0.0448 (observed
data), wR = 0.0739 (all data), GOF = 1.1177. Minimal/maximal
residual electron density –0.32/0.46 eÅ–3. Chebychev polynomial
weights[54] were used to complete the refinement. Plots were pro-
duced using Ortep3 for Windows.[55]
7,28-Bis(tert-butylsulfanyl)-37-ethoxy-36,38-dioxaheptacyclo-
[32.5.2.112,16.119,23.04,9.026,31.035,39]tritetraconta-1(39),4,6,8,
12(43),13,15,19(42),20,22,26,28,30,34,40-pentadecaene-
2,10,17,24,32-pentayne (6): Pd(PPh3)4 (123 mg, 0.11 mmol) and
CuI (21 mg, 0.11 mmol) were added to a degassed solution of com-
pound 13 (95 mg, 0.11 mmol) in a mixture of toluene (500 mL) and
iPr2NEt (1.5 mL). The resulting solution was stirred at room temp.
overnight and the solvents were evaporated. Flash chromatography
(SiO2, hexane/CH2Cl2, 65:35) afforded 6 (34 mg, 42%) as a yellow
solid; m.p. above 250 °C (decomposition). Rf = 0.28 (SiO2, hexane/
CCDC-737782 contains the supplementary crystallographic data
(excluding structure factors) for compound 6. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
1
3
CH2Cl2, 50:50). H NMR (400 MHz, CDCl3): δ = 1.20 (t, JH,H
=
Electrochemistry: All electrochemical measurements were per-
7.0 Hz, 3 H, CH3), 1.34 [s, 18 H, C(CH3)3], 3.71 (q, 3JH,H = 7.1 Hz, formed with an Autolab PGSTAT12 (Metrohm) and a conven-
2 H, OCH2), 7.18 (s, 2 H), 7.37 (t, JH,H = 7.6 Hz, 2 H), 7.38 (s, 1
3
tional three-electrode system comprising a glassy carbon (GC)
6148
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Eur. J. Org. Chem. 2009, 6140–6150