5
3
1
.06 (m, 8H), 4.91 (m, 6H), 4.54–4.37 (m, 20H), 4.18–4.16 (m,
NaOH and 10 ml H
2
O
2
(35%) were added, the mixture was stirred
1
3
H), 4.10–3.78 (m, 25H), 3.62–3.43 (m, 14H). C-NMR (CDCl
3
,
overnight at rt. 150 ml CH
extracted with CH Cl (3 ¥ 10 ml), the combined organic phases
were washed with sat. NH Cl (3 ¥ 50 ml) and brine 50 ml. The
residue was purified by flash chromatography, EtOAc:pentane, 1:4.
The desired product 13 appeared at R
= 0.28, in 25% yield (0.65 g),
and the diol 14 R 0.12, 54% yield (1.42 g), (TLC: EtOAc:pentane,
1:3) as colourless foams. 13: H-NMR (CDCl
2
Cl
2
was added and the water phase was
00 MHz) d : 139.4, 139.3, 138.4, 138.3, 138.1, 138.0, (Cipso) 134.7
C
2
2
(
C
allyl), 128.2, 128.1, 127.9, 127.8, 127.7, 127.6, 127.5, 127.4, 127.3,
27.2, 126.9 (CAr), 116.870 (Callyl), 98.8, 98.7, 98.6 (C-1), 80.9,
9.5, 79.1, 79.0, 78.9, 78.8, 75.6, 75.5, 73.3, 73.3, 72.7, 72.7, 72.2,
4
1
7
7
2
f
1.4, 71.3, 68.9. MALDI-TOF, m/z calcd. for C154
H
164
O30Na:
f
1
516.1205, found: 2515.7367.
3
, 400 MHz) d :
H
7
.43–7.03, (m, 80H, Ph), 5.51 (dd, J = 2.9, J = 10.9, 2H), 5.35
A
D
A-F
A-F
6
6
,6 -Di-O-(but-2-ene-1,4-diyl)-2 , 3
,
(d, J = 3.6, 1H), 5.29 (d, J = 10.5, 2H), 5.23 (d, J = 3.6), 5.04
B,C,E,F
-hexadecakis-O-benzyl-a-cyclodextrin (10)
(d, J = 10.9, 1H), 5.01 (d, J = 10.9, 1H), 4.96–4.81 (m, 8H), 4.77
(
dd, J = 2.7, J = 9.7, 2H), 4.68 (d, J = 9.5, 1H), 4.65 (d, J = 9.4,
Compound 9 (2.98 g, 1.19 mmol) was dissolved in 350 ml CH
in a three-neck round bottomed flask with condenser, under N
2
Cl
2
,
.
1
3
1
d
H), 4.55–4.22 (m, 24H), 4.08–3.71 (m, 17H), 3.64–3.49 (m, 6H),
2
.48–3.21 (m, 10H), 3.17–3.10 (m, 2H), 2.78 (s, 1H, OH), 1.60–
.49 (m, 2H, CH
nd
Grubbs cat. (2 gen, 0.11 g, 0.13 mmol), dissolved in 10 ml
CH Cl was added dropwise under stirring. The mixture was
refluxed under N for 2.5 h, before the heater was turned off,
allowing cooling to rt. Pb(OAc) (0.10 g, 2.14 mmol) was added
and the mixture left stirring overnight. The reaction mixture
was filtered through silica, washed vigorously with CH Cl and
evaporated. The product was purified by flash chromatography
EtOAc:pentane, 1:4, to afford 2.60 g of 10 (88% yield) as a
colourless foam. H-NMR (CDCl
13
2
-CH
2
(OH)(CH
2
). C-NMR (CDCl
3
, 100 MHz)
2
2
C
: 139.7, 139.5, 139.4, 139.3, 138.8, 138.3, 138.2, 138.1, 137.9,
ipso), 128.3, 128.2, 128.1, 128.0, 127.9, 127.8, 127.6, 127.5, 127.4,
27.1, 127.0, 126.9, 126.7, 126.5, 126.1, (CAr), 100.9, 100.3, 98.6,
2
(
C
4
1
9
8
7
6
8.5, 97.9, 97.8 (C-1), 82.5, 82.2, 81.8, 81.6, 81.5, 81.2, 80.6, 80.6,
0.5, 80.4, 80.2, 80.1, 79.6, 78.8, 77.8, 77.6, 76.4, 76.0, 75.3, 74.2,
3.3, 73.1, 73.0, 72.6, 72.0, 71.8, 71.7, 71.6, 71.2, 70.6, 70.1, 69.2,
2
2
9.0, 33.0 (CH
2
-CH
31Na: 2506.0998 found: 2505.8652.
, 400 MHz) d : 7.37–7.04 (m, 80 H, Ph),
2
(OH)(CH )). MALDI-TOF, m/z calcd. for
2
1
3
, 400 MHz) d : 7.42–7.07 (m,
H
C
152
H
162
1
O
8
0H, Ph), 5.56 (m, 1H), 5.48 (m, 2H), 5.41 (m, 1H), 5.35 (d,
1
4: H-NMR (CDCl
3
H
J = 10.5, 1H), 5.26 (d, J = 10.5, 1H), 5.17 (d, J = 3.6, 1H),
5
5
.52 (m, 1H), 5.46 (m, 1H), 5.40 (m, 1H), 5.34 (m, 1H), 5.25–
.14 (m, 2H), 4.98–4.79 (m, 12H), 4.73–4.66 (m, 2H), 4.59–4.32
5
3
.07–4.96 (m, 4H), 4.93–4.72 (m, 10H), 4.66–4.59 (m, 1H), 4.56–
1
3
.76 (m, 43H), 3.70–3.61 (m, 2H), 3.58–3.32 (m, 14H). C-NMR
, 100 MHz) d : 139.7, 139.5, 139.4, 139.3, 139.2, 138.7,
38.3, 138.2, 138.1, 138,0, 137.8, (Cipso) 128.7, 128.4–125.9 (CAr
alken), 100.8, 99.4, 99.3, 98.5, (C-1) 82.3, 82.0, 81.7 81.2, 81.0, 80.8,
(m, 4H), 4.25–4.15 (m, 3H), 4.07–3.82 (m, 16H), 3.80–3.62 (m,
(
CDCl
1
C
3
C
6
1
1
1
1
H), 3.60–3.39 (m, 11H), 3.36–3.22 (m, 3H), 2.30 (bs, 2H, OH),
,
13
.56–1.44 (m, 4H, -CH
2
-CH
2
-). C-NMR (CDCl
3
, 100 MHz) d
C
:
39.3, 139.2, 139.1, 138.5, 138.4, 138.2, 138.1, 138.0, 137.8, (CIpso
28.3, 128.2, 128.0, 127.9, 127.8, 127.7, 127.6, 127.5, 127.4, 127.3,
27.2, 127.1, 127.0, 126.7, (CAr), 98.7, 98.6, 98.3, 98.1, 98.0, 97.9,
)
80.6, 80.6, 79.8, 79.6, 78.70, 78.5, 78.0, 77.8, 76.4, 75.9, 74.5, 73.2,
73.2, 73.1, 73.0, 72.9, 72.8, 72.6, 72.2, 71.8, 71.7, 71.5, 71.4, 71.3,
70.9, 69.9, 69.7, 69.2, 68.7, 68.6, 60.3. MALDI-TOF, m/z calcd.
(C-1), 81.3, 81.1, 81.0, 80.7, 80.5, 80.2, 80.1, 79.5, 79.1, 78.9, 78.3,
for C152
H
160
O
30Na: 2488.0892, found: 2487.7099.
7
7.8, 76.1, 75.9, 75.8, 75.7, 74.5, 73.3, 73.2, 72.8, 72.3, 72.3, 71.8,
1.6, 71.6, 71.4, 71.3, 71.0, 70.0, 69.3, 69.2, 68.9, 29.7 (CH ), 26.4
). MALDI-TOF, m/z calcd. for C152 31Na: 2508.1154
found: 2507.8845.
7
2
A
D
6
,6 -Di-O-(butane-1,4-diyl)-a-cyclodextrin (11)
(CH
2
164
H O
The capped CD 10 (0.16 g, 0.07 mmol) was dissolved in 20 ml
MeOH:EtOAc, 1:1. TFA (cat.) and Pd/C (10%, 0.12 g) were
A
D
A-F
A-F
added. The mixture was flushed with N
2
and afterwards H
2
6 ,6 -Di-O-(but-2-one-1,4-diyl)-2 , 3 ,
B,C,E,F
was introduced, and left stirring for 48 h. The reaction mixture
6
-hexadecakis-O-benzyl-a-cyclodextrin (15)
was filtered through celite, washed with water (3 ¥ 10 ml) and
Compound 13 (0.65 g, 0.03 mmol) was dissolved in 40 ml CH
under N , and Dess–Martin periodinane (0.56 g, 1.33 mmol) was
added and stirred at rt for 3 h. The mixture was diluted with 30 ml
Et O and a solution of 30 ml sat. NaHCO containing 1.30 g
Na was added and stirred for 1 h. The organic phase was
washed with sat. NaHCO (3 ¥ 20 ml) and water (2 ¥ 20 ml)
followed by drying with MgSO . The residue was purified by flash
chromatography, EtOAc:pentane, 1:4, to give 0.54 g of 15 (84%
2
Cl
2
EtOAc (3 ¥ 10 ml). Evaporation and freeze drying gave 0.07 g of
1
2
compound 11 (100% yield) as a colourless solid. H-NMR (D
2
O,
4
3
4
1
7
2
1
00 MHz) d
H
: 5.14–5.03 (m, 6H, H-1), 4.79 (m, 16H, OH), 4.20–
2
3
.58 (m, 33H), 3.58–3.49 (m, 3H), 3.47–3.33 (m, 4H), 1.77–1.46 (m,
1
3
2
S
2
O
3
H, O-CH
2
-CH
2
-). C-NMR (DMSO-d
6
, 100 MHz) d : 102.1,
C
3
01.5, 101.0 (C-1), 83.4, 82.0, 81.7, 81.2, 74.1, 73.2, 73.0, 72.9,
2.1, 72.0, 71.9, 71.7, 71.5, 70.7, 69.5, 68.4, 60.0, 59.9, 59.8, 59.2,
6.1 (-O-CH
4
2
-CH
2
-). MALDI-TOF, m/z calcd. for C40
66
H O30Na:
1
yield) as a colourless foam. R
f
= 0.38, EtOAc:pentane, 1:2.5. H-
049.3537, found: 1049.7639.
NMR (CDCl , 400 MHz) d
3
H
: 7.51–7.11 (m, 80H, Ph), 5.73 (m,
A
D
A-F
A-F
B,C,E,F
1H), 5.68–5.61 (m, 2H), 5.43–5.34 (m, 3H), 5.18–4.79 (m, 15H),
4.73–4.52 (m, 14H), 4.50–4.29 (m, 9H), 4.26–3.95 (m, 13H), 3.945–
3.74 (m, 8H), 3.74–3.65 (m, 3H), 3.63–3.51 (m, 5H), 3.44–3.35 (m,
6
,6 -Di-O-(2-hydroxy-butane-1,4-diyl)-2 , 3 , 6
-
A
hexadecakis-O-benzyl-a-cyclodextrin (13) and 6 -O-(4-
hydroxybutyl)-2 , 3 , 6
a-cyclodextrin (14)
A-F
A-F
B,C,E,F
-hexadecakis-O-benzyl-
1
3
3
H), 3.23 (m, 2H), 2.43–2.34 (m, 2H, CH
2
CO). C-NMR (CDCl ,
3
100 MHz) d
C
: 206.2 (C=O), 139.7, 139.5, 139.4, 139.3, 139.2,
Compound 10, (2.60 g, 0.25 mmol) dissolved in 30 ml THF, was
138.9, 138.7, 138.4, 138.3, 138.2, 138.1, 138.0, 137.8 (CIpso), 128.3,
128.2, 128.1, 128.0, 127.8, 127.7, 127.6, 127.5, 127.4, 127.3, 127.2,
126.9, 126.7, 126.6, 126.1 (CAr), 100.5, 100.3, 99.8, 99.0, 98.6, 96.9
added to 9-BBN (0.5M in THF, 32 ml, 16.0 mmol) and stirred for
◦
24 h at rt under N
2
. The mixture was cooled to 0 C, 8 ml 3M
This journal is © The Royal Society of Chemistry 2009
Org. Biomol. Chem., 2009, 7, 933–943 | 939