D. Jayaprakash, H. Sasai / Tetrahedron: Asymmetry 12 (2001) 2589–2595
2593
was stirred for 30 min and dry DMF (1.3 mL, 14.6
mmol, 2 equiv.) was slowly added. After being stirred
for 2 h the solution was allowed to warm to −20°C. It
was then poured into 1N HCl/ice (100 mL). The product
was extracted with ethylacetate. The organic layer was
(d, J=6.7 Hz, 1H), 5.05 (d, 6.7 Hz, 1H), 5.06 (d, 6.7 Hz,
1H), 5.20 (dd, J=10.9, 0.9 Hz, 1H), 5.70 (dd, J=17.6,
0.9 Hz, 1H), 6.65 (dd, J=17.6, 10.9 Hz, 1H), 7.12–7.40
(m, 8H), 7.55 (d, J=9 Hz, 2H), 7.83 (d, J=3.8 Hz, 2H),
7.87 (s, 1H), 7.91 (d, J=3.5 Hz, 1H), 7.94 (d, J=3.4 Hz,
13
washed with saturated NaHCO solution and dried over
1H); C NMR (CDCl ) l 55.8, 71.8, 72.1, 95.1, 95.2,
3
3
anhydrous Na SO The crude product was obtained
upon evaporation of the solvent as a pale yellow oil.
113.7, 117.2, 117.4, 121.1, 121.22, 123.9, 125.4, 125.8,
126.1, 126.2, 126.3, 126.5, 127.7, 127.9, 129.2, 129.3,
129.6, 129.7, 133.5, 133.7, 136.4, 136.9, 137.7, 152.5,
2
4.
Flash column chromatography afforded 4 as a colorless
2
8
+
solid (1.95 g, 67% yield): [h] +57.6 (c=0.45, CHCl3);
152.6; MS (FAB) m/z 521 ([M+H] ).
D
IR (Neat) 2827, 1689, 1591, 1234, 1145, 1070, 1010, 750
−
1 1
cm ; H NMR (CDCl ) l 3.14 (s, 3H), 3.19 (s, 3H), 4.97
4.7. (R)-6-(4-Vinylbenzyloxy)methyl-2,2%-dihydroxy-1,1%-
binaphthalene 7
3
(
d, J=6.7 Hz, 1H), 5.03 (d, J=12.9 Hz, 1H), 5.08 (d,
J=12.6 Hz, 1H), 5.13 (d, J=7.0 Hz, 1H), 7.08 (d, J=8.0
Hz, 1H), 7.20 (m, 2H), 7.33 (t, J=6.9 Hz, 1H), 7.56 (d,
J=9.0 Hz, 1H), 7.67 (d, J=9.1 Hz, 2H), 7.87 (d, J=8.1
Hz, 1H), 7.95 (d, J=9.1 Hz, 1H), 8.10 (d, J=9.0 Hz,
To an ice cooled solution of 6 (250 mg, 3.81 mmol) in
THF (2 mL) was added a THF solution of HCl (1 mL
conc HCl in 4 mL of THF). The solution was allowed to
warm to room temperature slowly. After stirring for 15 h
the solution was carefully poured into water (50 mL).
The product was extracted with ethylacetate, dried over
13
1
5
1
1
H), 8.37 (s, 1H), 10.10 (s, 1H); C NMR (CDCl ) l
3
5.8, 56.0, 94.6, 95.0, 116.8, 117.5, 120.0, 123.1, 124.0,
24.9, 126.4, 127.9, 131.0, 132.4, 134.5, 152.5, 155.2,
+
91.8; MS (EI) m/z 402 (M ).
anhydrous Na SO4 and concentrated. Flash column
2
chromatography (SiO2, n-hexane/ethylacetate 9/1)
afforded 7 (190 mg, 92% yield) as a colorless foamy
4
.5. (R)-6-Hydroxymethyl-2,2%-bis(methoxymethyloxy)-
,1%-binaphthalene 5
28
1
solid. [h]D −46.9 (c=0.484, CHCl ); IR (Neat) 3496,
3
1 1
−
2
854, 1618, 1596, 1141, 1014 cm ; H NMR (CDCl ) l
3
To an ice cooled solution of 4 (1.85 g, 4.6 mmol) in
4.57 (s, 2H), 4.65 (s, 2H), 5.04 (s, 2H), 5.21 (dd, J=10.9,
0.9 Hz, 1H), 5.70 (dd, J=17.6, 0.9 Hz, 1H), 6.65 (dd,
J=17.6, 10.9 Hz, 1H), 7.12 (d, J=8.6 Hz), 7.27–7.40 (m,
8H), 7.86 (d, J=3.3 Hz, 1H), 7.87 (s, 1H), 7.94 (d, J=4.5
THF/MeOH (1:1, 24 mL) was added NaBH (173 mg,
4
4
.6 mmol) and the solution stirred at this temperature
for 15 min. The mixture was then poured into water (100
mL) and the product extracted with ethylacetate. After
drying over anhydrous Na SO , the solution was con-
13
Hz, 1H), 7.97 (d, J=4.5 Hz, 1H); C NMR (CDCl ) l
3
71.9, 110.7, 110.8, 113.7, 117.6, 117.9, 123.9, 124.0,
124.4, 126.1, 127.1, 127.4, 127.5, 127.9, 128.3, 129.2,
129.3, 131.2, 131.3, 133.8, 136.4, 137.6, 152.5, 152.6; MS
2
4
centrated to afford 5 as a colorless foamy solid (1.63 g,
8%). A portion of the solid was purified by flash column
8
2
9
+
chromatography for analysis. [h] +57.0 (c=0.45,
CHCl ); IR (Neat) 3400, 2823, 1591, 1234, 1145, 1066,
(EI): m/z 432 (M ).
D
3
−
1 1
1
3
008, 748 cm ; H NMR (CDCl ) l 3.05 (s, 3H), 3.06 (s,
H), 4.70 (s, 2H), 4.87 (d, J=6.7 Hz, 2H), 4.96 (d, J=3.3
4.8. Synthesis of the polymer supported BINOL 8b
3
Hz, 1H), 4.99 (d, J=3.3 Hz, 1H), 7.02–7.17 (m, 4H), 7.23
t, J=6.7 Hz, 1H), 7.47 (d, J=9.0 Hz, 2H), 7.75 (s, 1H),
.77 (d, J=8.1 Hz, 1H), 7.82 (d, J=5.4 Hz, 1H), 7.86 (d,
To a toluene solution of 6 (0.625 mg in 2 mL) was added
AIBN (0.056 g) and styrene (0.55 mL, 4.8 mmol). The
solution was purged with argon thoroughly. Polymeriza-
tion was carried out for 48 h at 75°C. After cooling to
room temperature the polymer was first precipitated by
addition to methanol followed by hexane. The precipi-
tate was filtered and dried in vacuo at 50°C for 3 h to
(
7
1
3
J=5.4 Hz, 1H); C NMR (CDCl ) l 55.8, 65.4, 95.1,
3
9
1
1
5.2, 117.2, 117.4, 121.1, 121.2, 123.9, 125.3, 125.5,
25.6, 125.9, 126.2, 127.7, 129.2, 129.3, 129.6, 129.7,
33.4, 133.8, 136.3, 152.5, 152.6; MS (EI): m/z 404 (M ).
+
2
9
give the polymer 8b (0.915 g, 81% yield). [h] +21.1
D
4
.6. (R)-6-(4-Vinylbenzyloxy)methyl-2,2%-bis(methoxy-
(c=0.45, CHCl ); M =9585 [Mn=6761, PDI=1.4]; IR
3
w
−
1
1
methyloxy)-1,1%-binaphthalene 6
(Neat) 2848, 1598, 1238, 1149, 1014 cm ; H NMR
CDCl ) l 0.882 (br), 1.42 (br), 1.82 (br), 3.13 (br), 4.58
(
3
To an ice cooled solution of 5 (1.54 g, 3.81 mmol) in
THF/DMF (1:1, 40 mL) was added NaH (135 mg, 5.7
mmol, 1.5 equiv., as 60% purity in oil) and the mixture
was stirred at this temperature for 30 min. 4-Vinylben-
zylchloride (0.53 mL, 3.84 mmol) was then added drop-
wise at this temperature and the solution was allowed to
warm to room temperature. After stirring for 72 h the
mixture was poured carefully into water (100 mL). The
product was extracted with ethylacetate, dried over
anhydrous Na SO and concentrated. Flash column
(br), 4.97 (br), 5.06 (br), 6.56 (br), 7.15 (br), 7.55 (br),
7.91 (br).
4.9. Removal of the protecting groups in 8b
To an ice cooled solution of the polymer 8b (880 mg) in
THF (2 mL) was added a THF solution of HCl (1 mL
conc. HCl in 4 mL of THF). The solution was then
allowed to warm to room temperature. After being
stirred for 15 h the solution was poured into water (50
mL). The product was extracted with CH Cl , washed
2
4
chromatography (SiO2, hexane/ethylacetate 9/1)
2
2
27
afforded 6 as a colorless mass (1.386 g, 70% yield). [h]D
43.3 (c=1, CHCl ); IR (Neat) 2825, 1593, 1236, 1147,
with saturated NaHCO and precipitated into hexane
3
+
twice. The precipitated polymer 9b was dried in vacuo at
3
−
1
1
29
1
010 cm ; H NMR (CDCl ) l 3.13 (s, 3H), 3.15 (s, 3H),
50°C for 3 h (650 mg). [h]D −23.2 (c=0.45, CHCl3);
3
4.56 (s, 2H), 4.64 (s, 2H), 4.95 (d, J=6.7 Hz, 1H), 4.96
M =9085 [Mn=5345, PDI=1.7]; IR (Neat) 3022,
w