Helvetica Chimica Acta ± Vol. 88 (2005)
947
2
,2'-{[(1R,2R)-Cyclohexane-1,2-diyl]bis[(E)-nitrilomethylidyne]}bis[6-(tert-butyl)-4-[tris(3,3,4,4,5,5,6,6,
7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silyl]phenol] (21). As described for 20, with (1R,2R)-cyclohexane-1,2-
diamine-l-tartrate (29 mg, 0.11 mmol), K
O (0.5 ml). After dilution with H
400 MHz, C capillary): 1.06 ± 1.10 (m, 2 H, alkyl); 1.23 ± 1.27 (m, 12 H, CH
.71 (m, 2 H, alkyl); 1.93 ± 2.02 (m, 4 H, alkyl); 2.15± 2.27 (m, 6 CH CF
); 3.24 ± 3.26 (m, 2 CHÀN); 7.27 (s, 2
arom. H); 7.54 (s, 2 arom. H); 8.40 (s, 2 CHN).
)-6,6'-Dibromo-[1,1'-binaphthalene]-2,2'-diol (23). To a suspension of (S )-binol (22; 7.2 g, 25 mmol) in
(250 ml) under Ar, a soln. of Br (3.9 ml, 76 mmol) in CH Cl
(40 ml) was added at À 788 within 15 min.
The red soln. was stirred at À 788 for 30 min, and stirring was continued for a further 3 h at r.t. To remove the
excess of Br , a sat. Na SO
the org. phase dried (Na SO
2
CO
3
(30 mg, 0.22 mmol), 19 (345 mg, 0.22 mmol), THF(10 ml), and
1
H
2
2
O (100 ml), workup yielded 21 (380 mg, > 98%). Yellow oil. H-NMR
(
7
F
16, C
6
D
6
2
Si); 1.52 (s, 2 t-Bu); 1.67 ±
1
2
2
(
S
a
a
CH
2
Cl
2
2
2
2
2
2
3
soln. (50 ml) was added. The aq. phase was extracted with AcOEt (3 Â 50 ml) and
2
4
) and evaporated. Recrystallization of the residue from cyclohexane/AcOEt gave
1
2
3 (10.6 g, 95%). Colorless crystals. M.p. 2048. H-NMR (300 MHz, CDCl
3
): 5.01 (s, 2 OH); 6.96 (d, J 9.2, 2
arom. H); 7.38 (dd, J 8.9, 2.1, 2 arom. H); 7.40 (d, J 9.2, 2 arom. H); 7.90 (d, J 8.9, 2 arom. H); 8.06 (d, J
1
3
2
.1, 2 arom. H). C-NMR (100.6 MHz, CDCl
3
): 110.8; 118.1; 119.1; 126.0; 130.5; 130.6; 130.7; 131.0; 132.0; 153.1.
EI-MS: 444 (100, M ), 284 (18, [M À Br
2
] ), 256 (31), 226 (26). Anal. calc. for C20 : C 54.09, H 2.72;
2 2
H12Br O
found: C 54.32, H 2.88.
(
S
a
)-2,2'-Bis[(benzyloxy)methoxy]-6,6'-dibromo-1,1'-binaphthalene (24). To a 60% suspension of NaH in
hexane (210 mg, 5.20 mmol) in anh. THF(3 ml) under Ar was added a soln. of 23 (0.8 g, 1.7 mmol) in anh. THF
6 ml) at 08 within 10 min (! yellow). At 08, benzyl chloromethyl ether (840 ml, 6.10 mmol) was added
dropwise. After stirring for an additional 3 h at 08, the mixture was quenched with H O (10 ml). The aq. phase
was extracted with CH Cl ) and evaporated, and the residue subjected
(
2
2
2
(3 Â 12 ml), the org. phase dried (MgSO
4
to CC (cyclohexane/AcOEt 10 :1): 24 (1.2 g, 99%). Colorless crystals which can be recrystallized from
1
cyclohexane/AcOEt. M.p. 1148. H-NMR (300 MHz, CDCl
3
): 4.31 (ꢁdꢀ, J 11.7, 2 H, H
A
of PhCH
2
O); 4.37 (ꢁdꢀ,
O); 6.99
J 11.8, 2 H, H
B
of PhCH
2
O); 5.09 (ꢁdꢀ, J 6.9, 2 H, H
A
of OCH
2
O); 5.18 (ꢁdꢀ, J 7.0, 2 H, H
B
of OCH
2
(
d, J 9.1, 2 arom. H); 7.03 ± 7.07 (m, 2 arom. H); 7.21 ± 7.27 (m, 4 arom. H); 7.66 (d, J 9.1, 2 arom. H); 7.88 (d,
13
J 9.1, 2 arom. H); 8.04 (d, J 2.1, 2 arom. H). C-NMR (100.6 MHz, CDCl
3
): 69.9; 92.8; 118.1; 120.8; 127.3;
1
27.8; 128.4; 128.8; 129.9; 130.0; 131.0; 132.5; 137.1; 153.0. EI-MS: 683 (4, M ), 654 (4), 624 (12). Anal. calc. for
36 2 4
C H28Br O : C 63.18, H 4.12; found: C 62.88, H 4.25.
(
S
a
)-2,2'-Bis[(benzyloxy)methoxy]-6,6'-bis[tris(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)sil-
F
yl]-1,1ꢀ'-binaphthalene (25; R C
8
F17). A soln. of 24 (6.2 g, 9.1 mmol) in anh. THF(80 ml) under Ar was
cooled to À 788, and 1.6m t-BuLi in hexane (22.0 ml, 37.3 mmol) was added within 30 min. After additional
stirring of the orange soln. at À 788 for 1.5 h, a soln. of 17 (26.4 g, 18.2 mmol) in dry perfluorohexane (60 ml)
was added. Stirring at À 788 was continued for 2 h. Then the dry-ice/acetone bath was removed and vigorous
4 2 2
stirring continued until r.t. was reached. A sat. aq. NH Cl soln. (80 ml) was added, the THFevaporated, CH Cl
(
100 ml) added, and the mixture extracted with perfluorohexane (6 Â 25 ml). After evaporation of the fluorous
solvent, the crude product was adsorbed on silica gel (25 g) with Et O (50 ml) and subjected to CC
cyclohexane/AcOEt 20 :1): 25 (18.0 g, 61%). Colorless viscous oil. TLC (cyclohexane/AcOEt 10 :1): R 0.25.
); 4.31 (ꢁdꢀ, J 12.0, 2 H,
of OCH
O); 5.16 (ꢁdꢀ, J 6.9,
O); 7.02 (m, 4 arom. H); 7.17 ± 7.28 (m, 6 arom. H); 7.44 (d, J 8.6, 2 arom. H); 7.76 (d, J 9.0, 2
2
(
f
1
H-NMR (400 MHz, C
of PhCH
); 4.36 (ꢁdꢀ, J 12.0, 2 H, H
H, H of OCH
arom. H); 8.05 (d, J 9.5, 2 arom. H); 8.20 (s, 2 arom. H). CI-MS: 3263 (2, M ), 2816 (7), 1387 (16), 1350 (19),
017 (100), 979 (86), 940 (13).
6
F
14, C
6
D
6
capillary): 1.12 ± 1.19 (m, 6 CH
2 2 2
Si); 2.33 (m, 6 CH CF
H
2
A
2
B
of PhCH
2
); 5.04 (ꢁdꢀ, J 6.9, 2 H, H
A
2
B
2
1
(
S
a
)-6,6 À -Bis[tris-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silyl][1,1'-binaphthalene]-2,2'-
F
F
diol (26; R C
8
F
17). To a soln. of 25 (R C
8
F
17; 1.9 g, 0.6 mmol) in THF(180 ml) at r.t. was added conc. HCl
O (80 ml) was added and the org. solvent evaporated. AcOEt
soln. (15 ml). After stirring under reflux for 6 h, H
2
(
90 ml) was added, the mixture extracted with perfluorohexane (6 Â 30 ml), the fluorous solvent evaporated,
and the crude product adsorbed on silica gel (4 g) with Et
1
C
arom. H); 8.11 (d, J 9.0, 2 arom. H); 8.22 (s, 2 arom. H). MALDI-TOF-MS: 3022 (M ), 1710, 1271, 1082, 1066.
2
O (20 ml) and subjected to CC (cyclohexane/AcOEt
1
0 :1 ! 4 :1): 26 (1.45 g, 80%). Colorless solid. TLC (cyclohexane/AcOEt 4 :1): R
f
0.25. H-NMR (400 MHz,
6
F
14, C
6
D
6
capillary): 1.31 ± 1.45 (m, 6 CH
2
Si); 2.20 ± 2.37 (m, 6 CH
2
CF
2
); 7.24 (m, 4 arom. H); 7.51 (d, J 9.0, 2
(
S
a
)-6,6'-Bis[tris(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silyl][1,1'-binaphthalene]-2,2'-diyl
F
F
Bis(trifluoromethylsulfonate (27; R C
8
F
17). To a soln. of 26 (R C
8
F
17; 1.6 g, 0.53 mmol) in a mixture of
O (218 ml,
O (30 ml) and
(30 ml) were added, and the mixture was extracted with perfluorohexane (4 Â 15 ml). The fluorous
CH Cl
1
CH Cl
2
2
(20 ml) and BTF(12 ml) was added pyridine (150 ml, 1.86 mmol). After cooling to 08, Tf
2
.32 mmol) was added. The mixture was stirred at 08 for an additional 4 h. After evaporation, H
2
2
2