Molecular Rods
FULL PAPER
9H-Fluoren-9-ylmethyl
15-hydroxy-7,11,18,21-tetraoxa-3-azatrispiro-
1122, 1108, 1082, 1054, 1034, 971, 920, 907, 895 cmꢀ1; HRMS: m/z: calcd
for C21H30O7: 394.1992, found: 394.1991 [M]+.
[5.2.2.5.2.2]henicosane-3-carboxylate (14m): TMSOTf (15 mL, 0.08 mmol)
was added to an ice cooled solution of ketone 4b (0.76 g, 2.36 mmol) and
13 (1.00 g, 2.35 mmol) in anhydrous Et2O and stirred at 08C until com-
plete conversion of 4b controlled by TLC. Ketone 10c (0.55 g,
2.35 mmol) was added and the mixture was stirred at 08C until complete
conversion of 4b controlled by TLC. The solvent was removed in vacuo
and the resulting residue was purified by flash chromatography (CH2Cl2/
MeOH 100:4) yielded 14m as a yellow solid (0.38 g, 0.71 mmol, 30%),
14i as a white solid (0.52 g, 0.70 mmol) and 12g as a white solid (0.10 g,
2-(Trimethylsilyl)ethyl 15-hydroxy-7,11,18,21-tetraoxatrispiro[5.2.2.5.2.2]-
henicosane-3-carboxylate (15c): According to GP 5 trispirane 14c (1.52 g,
2.64 mmol) was treated with DDQ (0.70 g, 3.08 mmol) yielded 15c with-
out further purification as a yellow solid (1.20 g, 2.63 mmol, 99%, calcu-
1
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lated by H NMR). H NMR (300 MHz, CDCl3): d=0.00 (s, 9H), 0.94 (t,
3J=8.5 Hz, 2H), 1.42 (dt, 3J=12.6, 4.1 Hz, 2H), 1.50–1.83 (m, 10H),
2.02–2.14 (m, 4H), 2.26 (tt, 3J=10.6, 4.0 Hz, 1H), 3.69 (dd, 3J=8.6,
7.7 Hz, 8H), 3.76 (m, 1H), 4.11 ppm (t, 3J=8.5 Hz, 2H); 13C NMR
(75.5 MHz, CDCl3): d=ꢀ1.5, 17.2, 24.7, 28.6, 28.8, 30.5, 30.8, 31.1, 32.8,
42.0, 62.5, 63.2, 63.3, 63.4, 63.7, 68.4, 97.7, 97.9, 175.4 ppm; IR: n˜ =3356,
3295, 2867, 1721, 1599, 11576, 458, 1443, 1380, 1340, 1312, 1249, 1204,
1
0.23, 10%). H NMR (300 MHz, CDCl3): d=1.57 (m, 2H), 1.71–1.77 (m,
1H+4H), 1.97 (m, 1H), 1.99–2.08 (m, 2H), 2.24 (ddd, 2J=14.6, 3J=7.2,
6.1 Hz, 1H), 2.58 (ddd, 2J=14.6, 3J=8.6, 6.1 Hz, 1H), 3.46 (brs, 4H),
3
3
1162, 1127, 1092, 1037, 911, 860, 832 cmꢀ1
; HRMS: m/z: calcd for
3.72 (brs, 8H), 4.17 (m, 1H), 4.22 (t, J=6.9 Hz, 1H), 4.40 (d, J=6.8 Hz,
2H), 7.29 (dt, 3J=7.4, 4J=1.3 Hz, 2H), 7.38 (t, 3J=7.4 Hz, 2H), 7.54 (d,
3J=7.5 Hz, 2H), 7.74 ppm (d, 3J=7.5 Hz, 2H); 13C NMR (75.5 MHz,
CDCl3): d=28.6, 30.3, 31.6, 32.3, 32.8, 33.6, 37.1, 40.5, 47.2, 63.0, 63.3,
63.4, 67.1, 68.1, 96.7, 97.9, 119.8, 124.8, 126.9, 127.5, 141.2, 143.8,
155.0 ppm; HRMS: m/z: calcd for C31H38NO7: 536.2648, found: 536.2657
[M]+.
C23H41O7Si: 457.2616, found: 457.2617 [M]+.
2-(Trimethylsilyl)ethyl 15-oxo-7,11,18,21-tetraoxatrispiro[5.2.2.5.2.2]heni-
cosane-3-carboxylate (16c): According to GP 1a alcohol 15c (1.15 g,
2.52 mmol) was treated with DMP (1.17 g, 2.76 mmol). Purification by
flash chromatography (CH2Cl2/MeOH 100:2) yielded 16c as a white solid
(0.93 g, 2.05 mmol, 81%). 1H NMR (300 MHz, CDCl3): d=0.00 (s, 9H),
0.93 (t, 3J=8.5 Hz, 2H), 1.42 (dt, 3J=12.5, 4.3 Hz, 2H), 1.61–1.74 (m,
2H), 1.77–1.83 (m, 2H), 2.06–2.14 (m, 6H), 2.26 (tt, 3J=10.7, 4.3 Hz,
1H), 2.34–2.38 (m, 4H), 3.70 (m, 8H), 4.11 ppm (t, 3J=8.5 Hz, 2H);
13C NMR (75.5 MHz, CDCl3): d=ꢀ1.5, 17.2, 24.7, 30.8, 30.9, 31.0, 32.8,
36.8, 42.0, 62.5, 63.1, 63.3, 64.0, 97.0, 97.8, 175.2, 210.3 ppm; IR: n˜ =2956,
2902, 2866, 1444, 1418, 1362, 1342, 1312, 1184, 1164, 1125, 1088, 1066,
15-Hydroxy-7,11,18,21-tetraoxatrispiro[5.2.2.5.2.2]henicos-3-yl
(15a): According to GP 5 trispirane 14a (1.81 g, 3.40 mmol) was treated
with DDQ (0.85 g, 3.74 mmol) yielded 15a as a white solid (0.79 g,
pivalate
1
1.92 mmol, 56%). M.p. 132–1348C; H NMR (300 MHz, CDCl3): d=1.15
(s, 9H), 1.50–2.06 (m, 16H), 3.68–3.72 (m, 8H), 3.75 (m, 1H), 4.85 ppm
(m, 1H); 13C NMR (75.5 MHz, CDCl3): d=26.7, 27.1, 28.1, 28.3, 28.6,
28.7, 30.4, 32.8, 38.8, 63.2, 63.3, 63.5, 63.6, 68.4, 69.6, 97.8, 98.0,
177.9 ppm; IR: n˜ =2959, 2868, 1726, 1478, 1460, 1442, 1373, 1337, 1249,
1232, 1200, 1163, 1141, 1282, 1096, 1058, 971, 950, 932, 911 cmꢀ1; HRMS:
m/z: calcd for C22H36O7: 412.2461, found: 412.2460 [M]+.
1036, 934, 896, 834, 861, 979, 966 cmꢀ1
; HRMS: m/z: calcd for
C23H38NaO7Si: 477.2285, found: 477.2285 [M+Na]+.
2-Nitrobenzyl 15-hydroxy-7,11,18,21-tetraoxatrispiro[5.2.2.5.2.2]henico-
sane-3-carboxylate (15d): According to GP 5 trispirane 14d (4.30 g,
7.03 mmol) was treated with DDQ (1.75 g, 7.71 mmol). Purification by
Flash Chromatography (CH2Cl2/MeOH 10:1) yielded 15d as a white
solid (1.60 g, 3.26 mmol, 46%). 1H NMR (300 MHz, CDCl3): d=1.49 (dt,
3J=12.4, 3.3 Hz, 2H), 1.66–1.83 (m, 8H), 1.90–2.07 (m, 4H), 2.17–2.24
(m, 2H), 2.47 (tt, 3J=10.6, 4.1 Hz, 1H), 3.70 (dd, 3J=8.5, 8.5 Hz, 8H),
3.76 (m, 1H), 5.46 (s, 2H), 7.43–7.54 (m, 2H), 7.62 (dt, 3J=7.7, 4J=
1.1 Hz, 1H), 8.06 ppm (dd, 3J=8.0, 4J=1.1 Hz, 1H); 13C NMR
(75.5 MHz, CDCl3): d=24.7, 28.6, 28.8, 30.5, 30.8, 31.0, 32.8, 41.9, 62.9,
63.2, 63.4, 63.6, 68.4, 97.6, 97.9, 125.0, 128.9, 129.0, 132.1, 133.6, 147.6,
174.4 ppm; IR: n˜ =3261, 2936, 2868, 1724, 1531, 1445, 1376, 1353, 1340,
1316, 1252, 1038, 1204, 1166, 1094, 1014, 982, 930, 911, 726 cmꢀ1; HRMS:
m/z: calcd for C25H34NO9: 492.2234, found: 492.2233 [M]+.
15-Oxo-7,11,18,21-tetraoxatrispiro[5.2.2.5.2.2]henicos-3-yl pivalate (16a):
According to GP 1a alcohol 15a (1.16 g, 2.81 mmol) was treated with
DMP (1.31 g, 3.09 mmol). Purification by flash chromatography (CH2Cl2/
MeOH 100:4) yielded 16a as a pale yellow solid (1.13 g, 2.75 mmol,
98%). M.p. 141–1488C; 1H NMR (300 MHz, CDCl3): d=1.15 (s, 9H),
1.70 (m, 4H), 1.82 (m, 4H), 2.10 (dd, 3J=7.0, 7.0 Hz, 4H), 2.37 (dd, 3J=
7.0, 7.0 Hz, 4H), 3.76–3.77 (m, 8H), 4.82 ppm (m, 1H); 13C NMR
(75.5 MHz, CDCl3): d=26.7, 27.1, 28.2, 30.9, 32.8, 36.8, 38.8, 63.2, 63.4,
63.9, 69.5, 97.0, 97.9, 177.9, 210.4 ppm; IR: n˜ =2963, 2937, 2867, 1709,
1478, 1441, 1426, 1378, 1321, 1283, 1254, 1231, 1197, 1170, 1145, 1121,
1086, 1033, 931, 901 cmꢀ1; HRMS: m/z: calcd for C22H34O7: 410.2305,
found: 410.2303 [M]+.
Allyl 15-hydroxy-7,11,18,21-tetraoxatrispiro[5.2.2.5.2.2]henicosane-3-carb-
oxylate (15b): According to GP 5 trispirane 14b (4.15 g, 8.03 mmol) was
treated with DDQ (2.01 g, 8.85 mmol). Purification by flash chromatogra-
2-Nitrobenzyl 15-oxo-7,11,18,21-tetraoxatrispiro[5.2.2.5.2.2]henicosane-3-
carboxylate (16d): According to GP 1a alcohol 15d (1.55 g, 3.15 mmol)
was treated with DMP (1.47 g, 3.47 mmol). Purification by flash chroma-
tography (CH2Cl2/MeOH 10:1) yielded 16d as a white solid (1.50 g,
3.06 mmol, 97%). 1H NMR (300 MHz, CDCl3): d=1.49 (dt, 3J=12.6,
4.1 Hz, 2H), 1.67–1.80 (m, 2H), 1.85–1.91 (m, 2H), 2.07–2.19 (m, 6H),
2.34–2.40 (m, 4H), 2.47 (tt, 3J=12.4, 4.1 Hz, 1H), 3.71 (s, 2H), 3.76 (s,
6H), 5.47 (s, 2H), 7.43–7.54 (m, 2H), 7.62 (dt, 3J=7.7, 4J=1.1 Hz, 1H),
8.06 ppm (dd, 3J=8.0, 4J=1.1 Hz, 1H); 13C NMR (75.5 MHz, CDCl3):
d=24.7, 30.8, 30.9, 31.0, 32.9, 36.8, 41.9, 62.9, 63.1, 63.3, 63.9, 97.0, 97.7,
125.0, 128.8, 129.1, 132.0, 133.6, 147.6, 174.3, 210.4 ppm; IR: n˜ =2958,
2921, 2894, 2854, 1709, 1439, 1382, 1367, 1340, 1318, 1275, 1257, 1180,
phy (CH2Cl2/MeOH 100:4) yielded 15b as
a white solid (1.68 g,
4.24 mmol, 53%). 1H NMR (300 MHz, CDCl3): d=1.41 (dt, 3J=12.8,
3.6 Hz, 2H), 1.49–1.85 (m, 10H), 2.01–2.15 (m, 4H), 2.37 (tt, 3J=10.5,
4.5 Hz, 1H), 3.66–3.72 (m, 8H), 3.76 (m, 1H), 4.53 (dt, 3J=5.6, 1.5 Hz,
2H), 5.22 (tdd, 2J=1.3, 3J=10.5, 4J=1.5 Hz, 1H), 5.26 (tdd, 2J=1.3, 3J=
17.2, 4J=1.5 Hz, 1H), 5.88 ppm (ddt, 3J=17.2, 10.5, 5.6 Hz, 1H);
13C NMR (75.5 MHz, CDCl3): d=24.7, 28.5, 28.8, 30.5, 30.8, 31.1, 32.8,
41.9, 63.2, 63.4, 63.6, 64.9, 68.3, 97.7, 97.9, 118.0, 132.2, 174.8 ppm; IR:
n˜ =3353, 3325, 3291, 3278, 2869, 1725, 1445, 1377, 1340, 1311, 1255, 1205,
1191, 1166, 1095, 1039, 1014, 910, 982, 929 cmꢀ1; HRMS: m/z: calcd for
C21H32O7: 396.2148, found: 396.2148 [M]+.
1167, 1108, 1001, 918, 896, 795, 731 cmꢀ1
; HRMS: m/z: calcd for
C25H31NO9: 489.1999, found: 489.1995 [M]+.
Allyl 15-oxo-7,11,18,21-tetraoxatrispiro[5.2.2.5.2.2]henicosane-3-carboxyl-
ate (16b): According to GP 1a alcohol 15b (1.63 g, 4.11 mmol) was treat-
ed with DMP (1.92 g, 4.53 mmol). Purification by flash chromatography
(CH2Cl2/MeOH 100:2) yielded 16b as a white solid (0.95 g, 2.41 mmol,
59%). 1H NMR (300 MHz, CDCl3): d=1.42 (dt, 3J=12.7, 3.6 Hz, 2H),
1.64–1.74 (m, 2H), 1.77–1.85 (m, 2H), 2.08–2.15 (m, 6H), 2.33 (tt, 3J=
10.4, 4.6 Hz, 1H), 2.34–2.37 (m, 4H), 3.69 (s, 2H), 3.75 (m, 6H), 4.53 (dt,
3J=5.7, 1.5 Hz, 2H), 5.18 (tdd, 2J=1.3, 3J=10.5, 4J=1.5 Hz, 1H), 5.26
(tdd, 2J=1.3, 3J=17.1, 4J=1.5 Hz, 1H), 5.86 ppm (ddt, 3J=17.1, 10.5,
5.7 Hz, 1H); 13C NMR (75.5 MHz, CDCl3): d=24.7, 30.8, 30.9, 31.0, 32.8,
36.8, 41.8, 63.0, 63.2, 63.9, 64.9, 97.0, 97.8, 118.0, 132.1, 174.7, 210.3 ppm;
IR: n˜ =3439, 2955, 2937, 2879, 1726, 1440, 1412, 1342, 1318, 1276, 1257,
Ethyl 15-hydroxy-7,11,18,21-tetraoxatrispiro[5.2.2.5.2.2]henicosane-3-carb-
oxylate (15e): According to GP 5 trispirane 14e (2.50 g, 4.95 mmol) was
treated with DDQ (1.27 g, 5.59 mmol). Purification by Flash Chromatog-
raphy (CH2Cl2/MeOH 100:5) yielded 15e as
a white solid (1.02 g,
2.65 mmol, 54%). 1H NMR (300 MHz, CDCl3): d=1.21 (t, 3J=7.2 Hz,
3H), 1.36–1.45 (m, 2H), 1.48–1.83 (m, 10H), 2.00–2.14 (m, 4H), 2.28 (tt,
3J=10.5, 4.1 Hz, 1H), 3.69 (dd, 3J=8.3, 8.3 Hz, 8H), 3.74 (m, 1H),
4.08 ppm (q, 3J=7.2 Hz, 2H); 13C NMR (75.5 MHz, CDCl3): d=14.2,
24.7, 28.6, 28.8, 30.5, 30.8, 31.1, 32.8, 41.9, 60.2, 63.2, 63.4, 63.6, 68.4, 97.7,
97.9, 175.2 ppm; IR: n˜ =3261, 2939, 2870, 1445, 1377, 1340, 1311, 1254,
1231, 1204, 1166, 1140, 1096, 1040, 1014, 983, 931, 909, 879, 827 cmꢀ1
;
HRMS: m/z: calcd for C20H33O7: 385.2221, found: 385.2222 [M]+.
Chem. Eur. J. 2007, 13, 4859 – 4872
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4869