ACCEPTED MANUSCRIPT
from hexane, to obtain (S,S)-10 (5.36g, 52%) as a white
4.2.5. (6S,16S)-6,16-didecyl-22-ethoxy-6,7,9,10,12,13,
29
powder. R (acetone-hexane 1:4) 0.27; [α]D =-11.5 (c 1.05,
15,16-octahydro-22H-dibenzo[n,q][1,4,7,10,13,16]
f
5
CH Cl ); mp. 55-57 °C; ν (neat) 3424, 2955, 2922, 2850,
pentaoxa-λ -phosphacyclooctadecin-22-one (S,S)-14
2
2
max
51
1
1
465, 1378, 1345, 1311, 1162, 1149, 1125, 1090, 1063,
049, 998, 982, 958, 908, 885, 842, 728, 720, 622, 542 cm ;
Ethyl bis(2-hydroxyphenyl)phosphinate (12)
(0.59 g,
−1
2.11 mmol), dodecyl-substituted tetraethylene glycol
ditosylate (R,R)-11 (1.50 g, 1.91 mmol) and finely powdered
anhydrous K CO (5 g, 36 mmol) were mixed with vigorous
δ (125 MHz CDC1 ) 0.86 (6H, t, J = 7 Hz, CH ); 1.23-1.46
H
3
3
(
m, 36H, CH ); 3.26-3.30 (m, 2H, OCH ); 3.50-3.54 (m, 2H,
2
2
2
3
OCH ); 3.60-3.68 (m, 10H, OCH , OH); 3.73–3.78 (2H, br
stirring in dry DMF (50 mL) under Ar. The temperature of
the vigorously stirred reaction mixture was raised to 50 °C
and kept at this temperature until TLC analysis showed the
total consumption of the starting materials (15 days). The
solvent was removed at 40 °C, then the residue was
dissolved in water (150 mL) and dichloromethane (80 mL).
The aqueous phase was shaken with 80 mL dichloromethane
three times. The combined organic phase was dried over
2
2
m, OCH). δ (125 MHz, CDCl ) 14.11 (CH ); 22.68; 25.63;
C
3
3
2
7
9.34; 29.59; 29.64; 29.74; 31.92; 32.88 (CH ); 70.08; 70.35;
2
+
0.44; 76.23 (OCH, OCH ). HRMS: MH found 475.43562;
2
C H O requires: 475.42842.
28
58
5
4
.2.2. (1R,11R)-1,11-Didecyl-3,6,9-trioxaundecane-1,11-
diol (R,R)-10
anhydrous MgSO , filtered and the solvent was removed.
4
Diol (R,R)-10 was prepared in the same way as described
The crude product was purified by coulumn cromatography
on silica gel using ethyl acetate–hexane mixtures (polarity
raised from 1:4 to 1:1) as eluents to give (S,S)-14 (0.37 g, 27
above for (S,S)-10 starting from (R)-epoxydedodecane (R)-7
26
(
11.0 g, 59.72 mmol). Yield: 7.93 g (56 %). [α]D =+12.1 (c
1
.08, CH Cl ). Other physical and spectroscopic data of
2
2
%
) as a colourless oil; Rf (CH Cl -MeOH 15:1) 0.88;
2 2
22
(R,R)-10 concurred with those of diol (S,S)-10.
[
α]D =-39.1 (c 0.74, CH Cl ); ν (neat) 3065, 2922, 2853,
2 2 max
1
1
590, 1577, 1473, 1444, 1367, 1278, 1243, 1220, 1142,
4
.2.3. (1S,11S)-1,11-Didecyl-3,6,9-trioxaundecane-1,11-
−1
088, 1040, 948, 754, 709, 566, 552, 514 cm ; δ (125
H
diyl-bis(4-methylbenzenesulfonate) (S,S)-11
MHz, CDCl ) 0.80 (t, J=6 Hz, 6H, CH ); 1.17-1.29 (m, 35H,
CH2, CH ); 1.35-1.42 (m, 4H, CH ); 2.52-2.58 (m, 1H,
OCH ); 2.82-2.99 (m, 5H, OCH ); 3.22-3.25 (m, 6H, OCH,
OCH ); 3.78-4.16 (m, 2H, OCH ); 4.30-4.33 (m, 2H, OCH );
3
3
Tosyl chloride (3.41 g, 17.89 mmol) and pyridine (10 ml)
was placed under Ar in a three necked flask fitted with a
stirring bar and dropping funnel. The mixture was cooled to
3
2
2
2
2
2
2
0
°C, and (S,S)-10 (2.50 g, 5.27 mmol) dissolved in pyridine
6
.84-6.98 (m, 4H, ArH); 7.26-7.37 (m, 2H, ArH); 7.77-8.14
(30mL) was added dropwise. After addition, the mixture was
(m, 2H, ArH). δ (125 MHz, CDCl ) 14,32 (d, J=1 Hz, CH );
C
3
3
allowed to warm up to room temperature. The mixture was
stirred for two days, and then the pyridine was removed. 10
%
1
2
5
7
6.50 (d, J=7 Hz, CH ); 22.65; 25.15; 25.21; 29.29; 29.31;
3
9.45; 29.53; 29.58; 29.62; 29.66; 31.87; 31.39; 32.09 (CH2);
Aqueous HCl solution (15 mL) and dichloromethane
9.84 (d, J=5 Hz, OCH ); 70.77; 70.89; 70.93; 71.34; 72.84;
2
(30 mL) were added to the residue. The resulting phases
3.43 (OCH ); 75.60; 76.68 (OCH); 111.71 (d, J=8 Hz,
2
were shaken thoroughly, and then they were separated. The
aqueous phase was shaken with 20 mL portions of
dichloromethane three times. The combined organic phase
ArC); 112.29 (d, J=8 Hz, ArC); 119.41 (d, J=4 Hz, ArC);
19.57 (d, J=5 Hz, ArC); 120.58 (d, J=84 Hz, ArC); 122.46
d, J=99 Hz, ArC); 132.67 (d, J=2 Hz, ArC), 133.15 (d, J=2
1
(
was dried over anhydrous MgSO , filtered and the solvent
4
Hz, ArC); 133.37 (d, J=4 Hz, ArC); 136.61 (d, J=7 Hz,
was removed. The crude product was purified by column
chromatography on silica gel using first dichloromethane-
methanol (200:1) and then ethyl acetate-hexane (8:1) as
ArC), 159.40 (d, J=4 Hz, ArC); 160.39 (d, J=5 Hz, ArC). δP
+
(121.5 MHz, CDCl ) 25.46. HRMS: MH 717.48525;
3
C H O P requires: 717.47809.
42
69
7
eluents to get (S,S)-11 (3.39 g, 82 %) as a colourless oil. R
f
22
(ethyl acetate-hexane 1:4) 0.14; [α]D =+5.3 (c 1.00,
4
1
.2.6. (6R,16R)-6,16-didecyl-22-ethoxy-6,7,9,10,12,13,
CH Cl ); ν (neat) 2922, 2853, 1598, 1496, 1458, 1401,
2
2
max
5,16-octahydro-22H-dibenzo[n,q][1,4,7,10,13,16]
1
7
359, 1306, 1291, 1188, 1175, 1119, 1097, 1019, 906, 813,
5
−1
pentaoxa-λ -phosphacyclooctadecin-22-one (R,R)-14
Crown ether (R,R)-14 was prepared in the same way as
described above for (S,S)-14 starting from ditosylate (S,S)-11
78, 664, 576, 553, 458 cm ; δ (125 MHz CDC1 ) 0.90 (t,
H
3
J = 7 Hz, 6H, CH ); 1.13-1.33 (m, 32H, CH ); 1.60-1.65 (m,
3
2
4
4
H, CH ); 2.46 (s, CH ); 3.49-3.61 (m, 12H, OCH );
2
3
2
2
5
(
(
(
1.50 g, 1.91 mmol). Yield: 0.38 g (28 %). [α]D =+38.5
c 0.77, CH Cl ). Other physical and spectroscopic data of
R,R)-14 concurred with those of crown ether (S,S)-14.
.60-4.65 (m, 2H, OCH); 7.34 (d, J = 8 Hz, 4H, ArH); 7.82
(d, J = 8.4 Hz, 4H, ArH). δ (125 MHz, CDCl ) 14.16 (CH );
2
2
C
3
3
2
3
1.66; 22.72; 24.78; 29.28; 29.36; 29.43; 29.53; 29.63;
1.47; 31.97 (CH ); 70.47; 70.85; 72.17; 81.99 (OCH,
2
+
OCH ); 127.89; 129.63; 134.46; 144.44 (ArC). HRMS: MH
4.2.7. (6S,16S)-2,20-Di-tert-butyl-6,16-didecyl-22-ethoxy-
6,7,9,10,12,13,15,16-octahydro-22H-dibenzo
2
found 783.45407; C H O S requires: 782.44613.
42
70
9 2
5
[n,q][1,4,7,10,13,16] pentaoxa-λ -phosphacyclo-octadecin-
2
2-one (S,S)-15
4
.2.4. (1R,11R)-1,11-Didecyl-3,6,9-trioxaundecane-1,11-
Crown ether (S,S)-15 was prepared in the same way as
described above for (S,S)-14 starting from ditosylate (R,R)-
1
hydroxyphenyl)-phosphinate (13) (0.83 g, 2.11 mmol).
Yield: 0.24 g (15 %). The product is a colourless oil. R
diyl-bis(4-methylbenzenesulfonate) (R,R)-11
Ditosylate (R,R)-11 was prepared in the same way as
described above for (S,S)-11 starting from diol (R,R)-10
1 (1.50 g, 1.91 mmol) and ethyl bis(5-tert-butyl-2-
43
25
(
(
3.20 g, 6.75 mmol). Yield: 7.93 g (85 %). [α]D =-5.6
c 1.05, CH Cl ). Other physical and spectroscopic data of
f
2
2
2
2
(CH Cl -MeOH 15:1) 0.81; [α] =+22.7 (c 1.02, CH Cl );
ditosylate (R,R)-11 concurred with those of (S,S)-11.
2 2 D 2 2
νmax (neat) 2953, 3032, 2922, 2854, 1599, 1487, 1466, 1394,
1
8
362, 1294, 1264, 1220, 1164, 1126, 1086, 1041, 948, 879,
−1
13, 669, 545, 503 cm ; δ (125 MHz, CDCl ) 0.86-0.90
H
3
(
1
m, 6H, CH ); 1.21-1.52 (m, 63H, CH CH ); 2.44-2.49 (m,
H, OCH ); 2.87-2.88 (m, 2H, OCH ); 2.93-2.96 (m, 1H,
2 2
3 2, 3
5