Immobilization of BINOL
3692±3705
solution of 9 (26.4 g, 71.0 mmol) in THF (160 mL). Workup and flash
column chromatography (hexane/CH2Cl2 2:1) afforded 10 (17.5 g, 57%) as
a white powder. M.p. 82.5 ± 83.58C; Rf (hexane/acetone 9:1): 0.53; 1H NMR
(400 MHz, CDCl3, 258C, TMS): d 4.39 (s, 2H; CH2Br), 5.00 (s, 4H;
2CH2O), 5.25 (dd, J(H, H) 10.9, 0.8 Hz, 2H; vinyl H), 5.75 (dd,
J(H, H) 17.6, 0.9 Hz, 2H; vinyl H), 6.52 (t, J(H, H) 2.2 Hz, 1H; arom.
H), 6.62 (d, J(H, H) 2.2 Hz, 2H; arom. H), 6.71 (dd, J(H, H) 17.6,
10.4 Hz, 2H; 2CHCH2), 7.34 ± 7.42 (m, 8H; arom. H); 13C NMR (100 MHz,
CDCl3, 258C): d 33.54, 69.92, 102.22, 108.21, 114.17, 126.54, 127.7, 136.3,
136.42, 137.4, 139.79, 160.03; IR (CHCl3): nÄ 3008 (w), 2870 (w), 1595 (s),
1513 (w), 1459 (m), 1407 (w), 1373 (m), 1160 (s), 1056 (m), 990 (m), 914 (m),
2H; 2CHCH2), 6.96 (dd, J(H, H) 9.2, 2.6 Hz, 2H; arom. H (BINOL)),
7.15 ± 7.17 (m, 4H; arom. H (BINOL)); 7.23 (d, J(H, H) 2.6, 2H; arom. H
(BINOL)); 7.47 ± 7.62 (m, 16H; arom. H), 7.66 (d, J(H, H) 8.7, 2H; arom.
H (BINOL); 13C NMR (125 MHz, CDCl3, 258C): d 12.77, 17.75, 17.83,
69.79, 107.35, 113.94, 118.66, 120.63, 121.76, 126.66, 127.12, 127.20, 127.62,
128.07, 129.69, 130.21, 136.33, 136.39, 136.67, 140.21, 140.35, 149.90, 154.84;
IR (CHCl3): nÄ 3006 (w), 2946 (s), 2866 (s), 1626 (w), 1595 (s), 1500 (s),
1463 (w), 1379 (m), 1351 (s), 1282 (m), 1170 (m), 1125 (m), 1080 (m), 1012
(s), 965 (w), 914 (w), 883 (m), 847 cmÀ1 (m); MALDI-TOF MS (2,5-DHB):
1015.8 [M] ; elemental analysis calcd (%) for C68H78O4Si2 (1015.52): C
80.43 H 7.74; found: C 80.25, H 7.70.
832 cmÀ1 (m); MS (EI): m/z (%): 436.2 (0.15) [M] , 355.3 (0.4), 233.1 (6),
Compound 14a: According to GP II, NaH (162 mg, 4.1 mmol) was added
to a solution of 2 (1.00 g, 1.62 mmol) in DMF (20 mL) at 08C. After stirring
at room temperature for 5 min and recooling to 08C, a solution of 7
(986 mg, 3.3 mmol) in DMF (20 min) was added, and the reaction mixture
was stirred at room temperature for 1 h. Workup and subsequent
purification of the crude product by flash column chromatography afforded
14a (810 mg, 46%) as a colorless foam. Rf (hexane/acetone 2:1): 0.54;
[a]2D0 À12.0 (c 1.00 in CHCl3); 1H NMR (500 MHz, CDCl3, 258C,
TMS): d 0.71 (d, J(H, H) 7.5 Hz, 18H; 6CH3), 0.78 (d, J(H, H)
7.5 Hz, 18H; 6CH3), 1.00 (m, 6H; 6CH(CH3)2), 5.05 (s, 4H; 2OCH2),
5.10 (d, J(H, H) 11.8 Hz, 2H; 2OCHH), 5.13 (d, J(H, H) 11.8 Hz, 2H;
2OCHH), 5.25 (dd, J(H, H) 10.9, 0.9 Hz, 2H; vinyl H), 5.74 (dd,
J(H, H) 17.6, 0.9 Hz, 2H; vinyl H), 6.72 (dd, J(H, H) 17.6, 10.9 Hz,
2H; 2CHCH2), 6.90 ± 6.94 (m, 2H; arom. H), 6.93 (dd, J(H, H) 9.2,
2.5 Hz, 2H; arom. H (BINOL)), 7.04 ± 7.11 (m, 6H; arom. H), 7.14 (d,
J(H, H) 9.2 Hz, 2H; arom. H (BINOL)), 7.16 (d, J(H, H) 8.8 Hz, 2H;
arom. H (BINOL)), 7.19 (d, J(H, H) 2.5 Hz, 2H; arom. H (BINOL)), 7.29
(dd, J(H, H) 7.9, 7.8 Hz, 2H; arom. H), 7.39 (d, J(H, H) 8.3 Hz, 4H;
arom. H), 7.41 (d, J(H, H) 8.3 Hz, 4H; arom. H), 7.64 (d, J(H, H)
8.8 Hz, 2H; arom. H (BINOL)); 13C NMR (125 MHz, CDCl3, 258C):
d 12.78, 17.74, 17.82, 69.77, 69.90, 107.37, 113.90, 114.06, 114.32, 118.65,
120.00, 120.62, 121.76, 126.42, 127.14, 127.60, 127.72, 129.61, 129.70, 130.22,
136.46, 136.56, 137.33, 138.93, 149.90, 154.82, 159.02; IR (CHCl3): nÄ 3008
(w), 2945 (m), 2866 (m), 1594 (s), 1499 (w), 1463 (w), 1408 (w), 1378 (m),
1350 (s), 1252 (s), 1156 (m), 1124 (m), 1081 (w), 1014 (s), 965 (w), 913 (w),
149.0 (2), 117.0 (100), 85.9 (33), 83.9 (55), 48.9 (21); elemental analysis calcd
(%) for C25H23O2Br (435.36): C 68.97, H 5.32; found: C 69.00, H 5.24.
3,5-Di[3,5-di(4-vinylbenzyloxy)benzyloxy]benzyl alcohol (11): A solution
of bromide 10 (15.0 g, 34.5 mmol), 3,5-dihydroxybenzyl alcohol (2.2 g,
15.7 mmol), 18-crown-6 (0.82 g, 3.1 mmol), and K2CO3 (4.77 g, 34.5 mmol)
in acetone (100 mL) was heated at 708C for 48 h. After cooling to room
temperature, CH2Cl2 (200 mL) and H2O (200 mL) were added to the
resulting suspension, the layers were separated and the organic layer was
dried over MgSO4. Evaporation of the solvents afforded a brown oil as
crude product, which was dissolved in toluene (40 mL). Upon slow addition
of hexane (20 mL), compound 11 (10.92 g, 82%) precipitated from the
solution as a white solid. M.p. 66.0 ± 67.08C; Rf (hexane/acetone 1:1): 0.51;
1H NMR (500 MHz, CDCl3, 258C, TMS): d 1.59 (t, J(H, H) 6.1 Hz,
1H; OH), 4.61 (d, J(H, H) 5.4 Hz, 2H; CH2OH), 4.97 (s, 4H; 2OCH2),
5.01 (s, 8H; 4OCH2), 5.25 (dd, J(H, H) 10.9, 0.7 Hz, 4H; vinyl H), 5.75
(dd, J(H, H) 17.6, 0.8 Hz, 4H; vinyl H), 6.51 (t, J(H, H) 1.7 Hz, 1 H;
arom. H), 6.54 (t, J(H, H) 1.8 Hz, 2H; arom. H), 6.58 (d, J(H, H)
2.2 Hz, 2H; arom. H), 6.66 (d, J(H, H) 2.2 Hz, 4H; arom. H), 6.71 (dd,
J(H, H) 17.6, 10.4 Hz, 4H; 4CHCH2), 7.35 ± 7.41 (m, 16H; arom. H);
13C NMR (125 MHz, CDCl3, 258C): d 62.71, 69.90, 69.97, 101.38, 101.65,
105.81, 106.38, 114.13, 126.44, 127.76, 136.34, 136.47, 137.39, 139.34, 143.44,
160.10, 160.15; IR (CHCl3): nÄ 3614 (w), 3008 (m), 1596 (s), 1514 (w), 1450
(m), 1407 (w), 1373 (m), 1295 (s), 1157 (s), 1050 (m), 1017 (w), 990 (m), 914
(m), 833 cmÀ1 (m); MALDI-TOF-MS (2,5-DHB): 871.7 [MNa] ; ele-
mental analysis calcd (%) for C57H52O7 (849.0): calcd: C 80.64, H 6.17;
found: C 80.38, H 6.41.
883 (m), 847 (w), 823 cmÀ1 (w); MS (FAB): m/z (%): 1075.4 (100) [M] ,
1074.4 (72), 9583 (5), 915 (4), 852 (7), 586 (5), 223 (13), 157 (5), 117 (92), 115
(29), 101 (7); elemental analysis calcd (%) for C70H82O6Si2 (1075.57): C
78.17, H 7.68; found: C 78.11, H 7.71.
3,5-Di[3,5-di(4-vinylbenzyloxy)benzyloxy]benzyl bromide (12): According
to GP I, CBr4 (8.1 g, 24.4 mmol) and PPh3 (6.4 g, 24.4 mmol) were added to
a solution of alcohol 11 (10.32 g, 12.2 mmol) in THF (70 mL) at 08C. After
stirring at 08C for 1 h and at room temperature for 48 h and working up, the
crude product was purified by flash column chromatography (hexane/
CH2Cl2 1:1 ! CH2Cl2) to give 12 (7.0 g, 63%) as a white solid. M.p. 86.5 ±
88.58C; Rf (CH2Cl2/hexane 2:1): 0.66; 1H NMR (500 MHz, CDCl3, 258C,
TMS): d 4.38 (s, 2H; CH2Br), 4.94 (s, 4H; 2OCH2), 5.01 (s, 8H; 4OCH2),
5.24 (dd, J(H, H) 10.9, 0.8 Hz, 4H; vinyl H), 5.74 (dd, J(H, H) 17.6,
0.8 Hz, 4H; vinyl H), 6.50 (t, J(H, H) 2.2 Hz, 1H; arom. H), 6.55 (t,
J(H, H) 2.2 Hz, 2H; arom. H), 6.60 (d, J(H, H) 2.2 Hz, 2H; arom. H),
6.64 (d, J(H, H) 2.2 Hz, 4H; arom. H), 6.71 (d, J(H, H) 17.6 Hz,
10.4 Hz, 4H; 4CHCH2), 7.34 ± 7.41 (m, 16H; arom. H); 13C NMR
(100 MHz, CDCl3, 258C): d 33.58, 69.88, 70.02, 101.71, 102.23, 106.41,
108.24, 114.11, 126.43, 127.73, 136.31, 136.45, 137.37, 139.09, 139.77, 159.96,
160.14; IR (CHCl3): nÄ 3008 (m), 1596 (s), 1514 (w), 1449 (m), 1407 (w),
1372 (m), 1295 (s), 1157 (s), 1048 (m), 990 (m), 914 (m), 832 cmÀ1 (m);
Compound 14b: According to GP III,
a solution of 14a (370 mg,
0.34 mmol) in THF (30 mL) was treated with TBAF ´ 3H2O (227 mg,
0.72 mmol) at 08C. Workup and flash column chromatography (hexane/
CH2Cl2 3:1) gave 14b (261 mg) as a colorless foam in quantitative yield. Rf
(hexane/acetone 1:1): 0.52; [a]2D0 55.7 (c 1.00 in CHCl3); 1H NMR
(500 MHz, CDCl3, 258C, TMS): d 4.89 (s, 2H; 2OH), 5.05 (s, 4H;
2OCH2), 5.12 (s, 4H; 2OCH2), 5.25 (dd, J(H, H) 10.9, 0.9 Hz, 2H; vinyl
H), 5.74 (dd, J(H, H) 17.6, 0.9 Hz, 2H; vinyl H), 6.72 (dd, J(H, H) 17.6,
10.9 Hz, 2H; 2CHCH2), 6.91 ± 6.93 (m, 2H; arom. H), 7.04 ± 7.09 (m, 8H;
arom. H), 7.26 ± 7.40 (m, 14H; arom. H), 7.81 (d, J(H, H) 8.9 Hz, 2H;
arom. H (BINOL)); 13C NMR (125 MHz, CDCl3, 258C): d 69.77, 70.00,
108.38, 111.28, 113.94, 114.10, 114.32, 118.18, 119.95, 120.17, 125.87, 126.42,
127.41, 128.70, 129.72, 130.06, 130.34, 136.43, 137.36, 138.56, 151.08, 155.52,
159.05; IR (CHCl3): nÄ 3533 (m), 3008 (w), 2872 (w), 1599 (s), 1513 (m),
1490 (m), 1450 (w), 1371 (m), 1263 (m), 1157 (m), 1120 (m), 1016 (m), 991
(w), 960 (w), 913 (w), 851 (m), 827 cmÀ1 (m); MS (FAB): m/z (%): 762.4
MALDI-TOF-MS (2,5-DHB): 933.9 [MNa] ; elemental analysis calcd
(%) for C57H51O6Br (911.9): C 75.07, H 5.64; found: C 75.26, H 5.75.
(100) [M] , 646 (6), 317 (5), 223 (27), 117 (76); elemental analysis calcd (%)
for C52H42O6 (762.89): C 81.87, H 5.55; found: C 81.87, H 5.52.
Compound 13: According to GP II, NaH (252 mg, 10.5 mmol) was added
slowly to a solution of 2 (2.65 g, 4.2 mmol) in DMF (20 mL) at 08C. After
stirring at room temperature for 5 min, the green suspension was recooled
to 08C with an ice-bath and a solution of 5 (2.52 g, 9.24 mmol) in DMF
(20 mL) was added. After stirring at room temperature for 1 h, H2O
(100 mL) was added and the reaction was worked up to give an orange oil
as crude product, which was purified by flash ccolumn chromatography
(hexane/CH2Cl2 2:1) to give 13 (1.82 g, 43%) as a colorless foam. Rf
(hexane/CH2Cl2 1:1): 0.54; [a]2D0 13.1 (c 0.98 in CHCl3); 1H NMR
(500 MHz, CDCl3, 258C, TMS): d 0.73 (d, J(H, H) 7.5 Hz, 18H; 6CH3),
0.81 (d, J(H, H) 7.5 Hz, 18H; 6CH3), 1.00 (m, 6H; 6CH(CH3)2), 5.17 (d,
J(H, H) 11.7 Hz, 2H; 2OCHH), 5.21 (d, J(H, H) 11.7 Hz, 2H;
2OCHH), 5.27 (dd, J(H, H) 10.9, 0.8 Hz, 2H; vinyl H), 5.78 (dd,
J(H, H) 17.6, 0.9 Hz, 2H; vinyl H), 6.75 (dd, J(H, H) 17.6, 10.9 Hz,
Compound 15a: According to GP II, NaH (158 mg, 3.9 mmol) was added
to a solution of 2 (1.00 g, 1.58 mmol) in DMF (10 mL) under ice-bath
cooling. After stirring at room temperature for 5 min, the green suspension
was recooled to 08C and a solution of 10 (1.38 g, 3.17 mmol) in DMF
(10 mL) was added. After stirring at room temperature for 1 h, workup, and
purification of the crude product by flash column chromatography (hexane/
CH2Cl2 1:1), 15a (1.06 g, 50%) was obtained as a colorless foam. Rf
(hexane/acetone 2:1): 0.51; [a]2D0 À11.2. (c 1.10 in CHCl3); 1H NMR
(400 MHz, CDCl3, 258C, TMS): d 0.72 (d, J(H, H) 7.5 Hz, 18H; 6CH3),
0.79 (d, J(H, H) 7.5 Hz, 18H; 6CH3), 0.99 (m, J(H, H) 7.5 Hz, 6 H ;
6CH(CH3)2), 5.02 (s, 8H; 4OCH2), 5.05 (d, J(H, H) 9.1 Hz, 2H;
2OCHH), 5.08 (d, J(H, H) 9.1 Hz, 2H; 2OCHH), 5.25 (dd, J(H, H)
10.9, 0.9 Hz, 4H; vinyl H), 5.74 (dd, J(H, H) 17.6, 0.9 Hz, 4H; vinyl H),
Chem. Eur. J. 2000, 6, No. 20
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
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3701