B. C. Gibb et al.
FULL PAPER
added by syringe pump over 64 h. The solution was then heated to 608Cfor
four days. After this time the DMA was removed under reduced pressure,
the mixture was partitioned between CHCl3 and water, and the organic
layer collected. The aqueous layer was washed twice with CHCl3, and the
organic layers were combined and dried with anhydrous MgSO4. The
solvent was reduced down to about 100 mL under reduced pressure. Silica
gel (ca. 50 mL) was then added to the solution, and the solvent removed
under reduced pressure. The dry silica was loaded on a 100% hexane silica
column, and the excess 3,5 diBr-benzal bromide eluted with 100% hexane.
The product was then eluted with 50% CHCl3/hexane, and the solvent
subsequently removed under reduced pressure. The crude product was then
recrystallized from CHCl3/hexane to give a 64% yield of the cavitand as a
white solid.
Large-scale synthesis of basket 3:[7a] DCC 2 (1 g, 0.53 mmol), K2CO3
(877 mg, 6.3 mmol), resorcinol (350 mg, 3.18 mmol), and pyridine
(65 mL) were added to a dried flask. Nitrogen was then bubbled through
the solution for five minutes, before CuO (505 mg, 6.3 mmol) was carefully
added. The flask was then fitted with a water condenser, and the stirring
solution heated to reflux (sand bath) for seven days. After this time the
solvent was removed under reduced pressure, and the resulting solid
suspended in chloroform and flushed through a silica plug with CHCl3
(100%). The solvent of the resulting solution was removed under reduced
pressure, and the crude product further purified by column chromatog-
raphy (mobile phase 50% CHCl3/hexane). The product was isolated as a
colorless solid in 78% yield (88% on the 250 mg scale).
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Synthesis of basket 4: DC C2 (100 mg, 5.30 Â 10À5 mol) was added to an
oven-dried round bottom flask containing pyridine (24 mL). K2CO3
(146.4 mg, 1.06 mmol) and 5-methyl resorcinol (65.8 mg, 0.53 mmol) were
added to this stirring solution. Nitrogen was bubbled through the mixture
for five minutes, before CuO (84.3 mg, 1.06 mmol) was added, and the
solution was heated to a vigorous reflux (sand bath) and stirred for seven
days. After cooling the solvent was removed under reduced pressure to give
a crude solid mixture that was suspended in CHCl3 and loaded onto a short
silica plug. Flushing with CHCl3 and removal of the solvent of the resulting
colorless solution gave the crude product. Chromatography (1:1 CHCl3/
hexane) and then recrystallization with CHCl3/hexane gave the pure
product 4 as a colorless solid in 88% yield.
m.p. > 2508C; 1H NMR (500 MHz, CDCl3): d 2.433 (s, 12H), 2.55 (m,
16H), 4.56 (s, 4H), 4.84 (t, J 8 Hz, 4H), 6.05 (s, 4H), 6.39 (t, J 2 Hz,
4H), 6.52 (d, J 2 Hz, 8H), 6.93 (t, J 2 Hz, 4H), 7.00 (d, J 2 Hz, 8H),
7.10 (m, 8H) 7.19 (m, 16H); MS: m/z: [MAg ] calcd 1845; found:
1845.97; elemental analysis calcd (%) for C116H88O16: C80.17, H 5.10;
found: C80.05, H 5.17.
Synthesis of basket 5: DC C2 (100 mg, 5.30 Â 10À5 mol) was added to an
oven-dried round bottom flask containing pyridine (24 mL). K2CO3
(146.4 mg, 1.06 mmol) and 2-methyl resorcinol (65.8 mg, 0.53 mmol) were
added to this stirring solution. Nitrogen was bubbled through for five
minutes before CuO (84.3 mg, 1.06 mmol) was added, and the solution was
heated to a vigorous reflux (sand bath) and stirred for 14 days. After
cooling the solvent was removed under reduced pressure to give a crude
solid mixture that was suspended in CHCl3 and loaded onto a short silica
plug. Flushing with CHCl3 and removal of the solvent of the resulting pale
yellow solution gave the crude product. Chromatography (1:1 CHCl3/
hexane) and then recrystallization with CHCl3/hexane gave the pure
product 5 as a colorless solid in 80% yield.
m.p. > 2508C; 1H NMR (500 MHz, CDCl3): d 1.64 (s, 12H), 2.53 (m,
16H), 4.50 (s, 4H), 4.81 (t, J 8 Hz, 4H), 5.93 (s, 4H), 6.48 (d, J 1 Hz,
8H), 7.04 (s, 4H), 7.09 (m, 8H), 7.14 (s, 4H), 7.20 (m, 20H), 7.40 (t, J 8 Hz,
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Acknowledgements
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This work was supported by the National Science Foundation (CHE-
0111133), the Donors of the Petroleum Research Fund, administered by
the American Chemical Society, and the Cancer Association of Greater
New Orleans (CAGNO). Z.R.L. thanks the LouisianaBoR for a fellow-
ship. Special thanks also to Richard B. Cole and the New Orleans Center
for Mass Spectrometry Research for carrying out mass analysis of hosts
3
5.
138
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