748
A.R. Abreu et al. / Tetrahedron 66 (2010) 743–749
Physical and spectroscopic data were in agreement with those
previously described.22
(S)-H8BINOL (5.2 g, 17.5 mmol), PPh3 (4.59 g, 17.5 mmol), and ben-
zyl alcohol (2.1 mL, 20 mmol), in dry THF (200 mL), a solution of
diethyl azodicarboxylate (DEAD) (7.7 mL, 40% in toluene,
17.5 mmol) was added dropwise. The reaction was kept with stir-
ring at room temperature, during 48 h. Then, the mixture was
evaporated under reduced pressure. The residue was redissolved in
dichloromethane and washed with water and brine. After partial
evaporation of the solvent at reduced pressure, the residue was
purified by silica gel column chromatography using CH2Cl2:
n-hexane (1:1) as eluent,and two fraction were collected. After
evaporation of the solvent of fraction 1, the solid was recrystallized
from toluene/n-hexane, to afford 9 as a white solid, yielding 5.4 g
(80%) of (S)-20-(benzyloxy)-5,50,6,60,7,70,8,80-octahydro-1,10-bina-
4.2.6. Synthesis of (1R,100R)-20,200-(propane-1,3- diylbis(oxy))bis-
(5,50,6,60,7,70,8,80-octahydro-1,10-binaphthyl-2-ol) 7. A solution of 3b
(1.88 mmol) in CHCl3/MeOH (3:1) in the presence of Pd/C 5% was
submitted to 35 bar of H2 along 72 h at the temperature of 35 ꢀC.
The reaction mixture was filtrated in Celite, and the residue was
washed with methanol. Then, the mixture was evaporated under
reduced pressure and the residue was purified by silica gel column
chromatography using dichloromethane as eluent. The desired
fraction was evaporated yielding (1R,100R)-20,200-(propane-1,3-
diylbis(oxy))bis(5,50,6,60,7,70,8,80-octahydro-1,10-binaphthyl-2-ol) as
a white powder. Yield 945.78 mg (80%); 1H NMR (400 MHz, CDCl3):
0
phthyl-2-ol (S)-BnH8BINOL (9): 1H NMR (400 MHz, CDCl3):
d 7.31–
d
¼7.08 (d, J¼8.3 Hz, 2H (H4)), 6.99 (d, J¼8.3 Hz, 2H, (H4 )), 6.71 (d,
7.10 (m, 5H), 7.03 (dd, J3¼13.5 Hz, J3¼8.4 Hz, 2H), 6.80 (dd,
J3¼8.3 Hz, J3¼3.5 Hz, 2H), 4.99 (s, 2H), 4.39 (bs, 1H), 2.76 (dd,
J1¼13.8 Hz, J3¼6.5 Hz, 4H), 2.41–2.03 (m, 4H), 1.80–1.52 (m, 8H)
0
J¼8.3 Hz, 2H, (H2)), 6.63 (d, J¼8.3 Hz, 2H, (H2 )), 4.37 (br s, 2H, (OH)),
0
3.80–3.66 (m, 4H,(OCH2)), 2.81–2.73- (m, 8H, (H8,8 )), 2.36–2.02 (m,
8H,, (H5,5 )), 1.83–1.34 (m, 18H, (H6,6 ,7,7 CH2)) ppm. 13C NMR
ppm. 13C NMR (101 MHz, CDCl3):
d 154.38, 150.18, 138.19, 137.66,
0
0
0
0
(101 MHz, CDCl3): 154.92(C2), 150.45(C2 ), 138.19(Arq), 136.46(Arq),
136.13, 130.90, 130.17, 129.35, 129.09, 128.33, 127.38, 126.54, 123.03,
122.80, 112.12, 111.28, 70.04, 29.38, 29.32, 27.36, 27.08, 23.22, 23.18,
23.07, 22.98 ppm. Mp 101–102 ꢀC. MS (ESI): m/z¼407.1982 (MþNa),
calcd for C27H28O2Naþ 407.1982.
After evaporation of the solvent of fraction 2, the solid was
recrystallized from toluene/n-hexane, to afford 10 as a white solid,
yielding 683 mg (10%) of (S)-2,20-bis(benzyloxy)-5,50,6,60,7,70,8,80-
octahydro-1,10-binaphthyl (10): 1H NMR (400 MHz, CDCl3):
130.71(Arq), 130.54(Ar–CH), 129.44(Ar–CH), 129.19 (Arq), 123.35
(Arq–Arq), 122.81(Arq–Arq), 113.09 (Ar–CH), 110.67 (Ar–CH), 64.74
(OCH2), 29.72 (CH2), 29.22 (CH2), 27.57 (CH2), 27.43 (CH2), 23.58
(CH2), 23.49 (CH2), 23.43 (CH2), ppm. MS (ESI): m/z¼651.3442
(MþNa), calcd. For C43H48O4Naþ 651.3445.
4.2.7. Tin acetal procedure.
4.2.7.1. (R)-4,4-Dibutyldinaphtho[2,1–d:10,20f][1,3,2]-dioxo-
stannepine 5. A round bottomed flask fitted with a Dean–Stark
head was charged with (R)-binaphthol (5 g, 1.75 mmol) and dibu-
tyltin oxide (4.3 g, 1.75 mmol) in 1,2-dichloroethane (100 mL), the
mixture was refluxed, under argon, with intermittent removal of
water azeotrope. The evolution of the reaction was carried fol-
lowing the disappearance of the hydroxyl vibrational IR signal
(3500 cmꢁ1) of binaphthol (ca. 4 h). The solvent was then removed
under reduced pressure giving a quantitative yield of product,
which was used without further purification. The physical and
spectroscopic data are in good agreement with those previously
reported in the lit.33
d
¼7.09–7.03 (m, 6H), 7.02–6.95 (m, 4H), 6.91 (d, J¼8.4, 2H), 6.66 (d,
J¼8.3, 2H), 4.86 (s, 4H), 2.67 (t, J¼5.7, 4H), 2,33–2.07 (m, 4H), 1.68–
1.48 (m, 8H) ppm. 13C NMR (101 MHz, CDCl3):
152.60, 137.12,
d
135.85, 127.50, 127.17, 127.08, 126.95, 126.00, 125.84, 125.64, 125.36,
109.90, 69.14, 28.45, 26.27, 22.23, 22.16 ppm. Mp 58–61 ꢀC. MS
(ESI): m/z¼497.2441 (MþNa), calcd for C34H34O2Naþ 497.2451.
4.2.9. (4S,5S)-4,5-Bis(((S)-20-(benzyloxy)-5,50,6,60,7,70,8,80-octahy-
dro-1,10-binaphthyl-2-yloxy)methyl)-2,2-dimethyl-1,3-dioxolane
11. To a suspension of sodium hydride (160 mg, 60% in paraffin,
4 mmol), in dry dimethylformamide (DMF) (10 mL, 0 ꢀC), a solution
of 9 (2.7 mmol), in dry DMF (5 mL), was added dropwise (30 min.).
A solution of the desired ditosylalkane 2d (1.3 mmol) in dry DMF
was then slowly added to the previous mixture at 0 ꢀC during 1 h.
After total addition of the desired ditosylalkane the reaction was
stirred along 6 h at 80 ꢀC. After cooling, water was added dropwise
(0 ꢀC) and the organic compound was extracted with CH2Cl2. The
organic layer was washed with water and brine solution, and the
concentrated organic phase was purified by flash chromatography
using CH2Cl2/nhexane (2:1) as eluent, yielding 743 mg of 11 (65%)
after evaporation of the solvent and recrystallized from AcOEt/
PriOH. (4S,5S)-4,5-bis(((S)-20-(benzyloxy)-5,50,6,60,7,70,8,80-octahydro-
1,10-binaphthyl-2-yloxy)methyl)-2,2-dimethyl-1,3-dioxolane (11): 1H
4.2.7.2. Synthesis of (R,R)-a,a
0-bis[20(2-hydroxy-1,10-binaph-
thyl)Oxy]-o-xylene 6. 1,2-Bis-(iodomethyl)-benzene, prepared by
reaction de dibromo derivative with NaI in acetone, (3 g, 8.22
mmol) dissolved in dry toluene, was added to a toluene solution of
5 (6.69 g, 13.7 mmol) (50 mL toluene) under inert atmosphere. The
reaction was kept at the temperature of 120 ꢀC during 72 h.
After cooling to room temperature, the mixture was treated
with a solution of HCl in dioxane (1.7 M) and then the solvent was
evaporated under reduced pressure. The crude was extracted with
in ethyl acetate and separated from the salts by filtration. The so-
lution was washed with water and brine and the resulting organic
phase was dried over MgSO4. The mixture was purified by flash
chromatography using CH2Cl2: n-hexane (3:1) as eluent. The crude
was recrystallized from toluene/n-hexane, yielding the desired
NMR (400 MHz, CDCl3):
d
7.20–7.04 (m, 6H), 6.98 (dd, J3¼17.8,
J3¼8.1 Hz, 8H), 6.67 (d, J¼8.3 Hz, 2H), 6.54 (d, J¼8.4 Hz, 2H), 4.74 (s,
4H), 3.80 (m, 2H), 3.72–3.38 (m, 4H), 2.86–2.60 (m, 8H), 2.42–2.18 (m,
4H), 2.18–2.00 (m, 4H), 1.78–1.48 (m, 16H), 0.97 (s, 6H) ppm. 13C NMR
(R,R)-
a
,
a
0-bis{20(2-hydroxy-1,10-binaphthyl)oxy}-o-xylene
7
as
(101 MHz, CDCl3): d 153.66, 153.55, 138.16, 136.73, 136.63, 129.96,
a white powder. Yield 1.85 g (40%); 1H NMR (300 MHz, CDCl3): 7.90
(t, J¼9.0 Hz, 4H), 7.80 (t, J¼9.0 Hz, 4H), 7.37 (d, J¼8.0 Hz, 2H), 7.26–
7.13 (m, 12H), 6.95–6.89 (m, 6H), 5.30 (br s, 2H), 4,75 (m, 4H) ppm.
129.93, 128.51, 128.40, 128.10, 127.01, 126.68, 126.29, 126.23, 110.97,
110.04, 109.30, 75.58, 70.09, 67.19, 29.47, 29.41, 27.23, 27.18, 26.33,
23.24, 23.20, 23.14 ppm. 75–77 ꢀC. MS (ESI): m/z¼917.4748 (MþNa),
calcd for C61H66O6Naþ 917.4752.
13C NMR (101 MHz, CDCl3):
d¼154.53,151.07,134.60,133.81,133.65,
130.72, 129.66, 129.47, 128.89, 128.29,127.97, 127.69, 127.10, 126.30,
124.85, 124.67, 124.26, 123.03, 117.28, 116.33, 115.65, 114.89,
68.83 ppm. Mp 92–93 ꢀC. (ESI): m/z¼697.2356 (MþNa), calcd for
C48H34O4Naþ 697.2349.
4.2.10. (10S,10S)-20,200-((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5 diyl)-
bis(methylene)bis(oxy)bis(5,50,6,60,7,70,8,80-octahydro-1,10-bibenzo-
benzen-2-ol) 12. A solution of 11 (1.88 mmol) in AcOEt/PriOH (3:1)
in the presence of Pd/C 5% was hydrogenated in a Parr apparatus at
3 bar for 48 h at room temperature. The reaction mixture was fil-
trated in Celite, and the residue was washed with methanol. After
evaporation of the solvent and recrystallized from toluene/
4.2.8. (S)-20-(Benzyloxy)- 5,50,6,60,7,70,8,80-octahydro-1,10-binaphthyl-
2-ol (S)-BnH8BINOL 9. The compound was synthesized by slightly
modifications of Mitsunobu reaction.26 To a stirred solution of