Nolan T. McDougal et al.
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charged with (S)-2,2’-dihydroxy-[1,1’]binaphthalenyl-3,3’-di-
carboxylic acid dimethyl ester[30] (180 mg, 0.44 mmol) and
Adamꢀs catalyst (PtO2 ·H2O, 18.1 mg, 0.074 mmol). The atmos-
phere of the flask was purged under vacuum and flushed with
H2 three times. The reaction was stirred under a balloon pres-
sure H2 atmosphere for 24 h. The reaction mixture was filtered
through a bed of Celite, diluted with CHCl3 (20 mL), and wash-
ed with excess water. The organic layer was washed with a sa-
turated aqueous NaHCO3 solution (10 mL), and dried over
Na2SO4. Concentration of the organic layer afforded (S)-2,2’-
dihydroxy-5,6,7,8,5’,6’,7’,8’-octahydro-[1,1’]binaphthalenyl-3,
3’-dicarboxylic acid dimethyl ester as a pale yellow powder;
yield: 174 mg (0.42 mmol, 95%); [a]2D1: ꢀ36.68 (c 1.00,
Na2SO4. Concentration of the organic layer afforded (R)-3,3’-
dibromo-2,2’-dimethoxy-5,6,7,8,5’,6’,7’,8’-octahydro-[1,1’]bi-
naphthalenyl as colorless crystals; yield: 3.8 g (7.9 mmol, 94%).
Characterization and spectroscopic data was in agreement
with lit. values.[20]
Representative Procedures for the Suzuki Coupling of
9 to Yield Compounds 10a – d
Procedure 1: (R)-3,3’-Bis-biphenyl-4-yl-2,2’-dimethoxy-5,6,
7,8,5’,6’,7’,8’-octahydro-[1,1’]binaphthalenyl (10d): Tris(di-
benzylideneacetone)dipalladium (46 mg, 0.05 mmol), tricyclo-
hexylphosphine (42 mg, 0.15 mmol), 4-biphenylboronic acid
(590 mg, 3.0 mmol), potassium fluoride (360 mg, 6.2 mmol),
and (R)-3,3’-dibromo-2,2’-dimethoxy-5,6,7,8,5’,6’,7’,8’-octahy-
dro-[1,1’]binaphthalenyl (480 mg, 1.0 mmol) were added to a
10 mL flask under an argon atmosphere. THF (2 mL) was add-
ed to the reaction flask, and the reaction mixture was refluxed
at 758C for 18 h. Upon cooling to room temperature, the reac-
tion mixture was diluted and filtered through a pad of silica gel
with EtOAc, and the washings were concentrated. The residue
was subjected to flash chromatography on silica gel and eluted
with hexane and toluene (1:1) to afford (R)-3,3’-bis-biphenyl-
4-yl-2,2’-dimethoxy-5,6,7,8,5’,6’,7’,8’-octahydro-[1,1’]binaph-
thalenyl as colorless crystals; yield: 510 mg (0.81 mmol, 81%);
1
CHCl3); H NMR (400 MHz, CDCl3): d¼10.64 (s, 2H), 7.61
(s, 2H), 3.90 (s, 6H), 2.68–2.84 (m, 4H), 2.38–2.48 (m, 2H),
2.10–2.20 (m, 2H), 1.58–1.80 (m, 8H); 13C NMR (75.0 MHz,
CDCl3): d¼170.9, 156.2, 144.8, 129.5, 128.3, 123.8, 109.9,
51.9, 29.0, 27.3, 22.6, 22.5; IR (thin film): n¼3019, 2400, 1670,
1521, 1440, 1316, 1216, 1046, 929, 755, 670 cmꢀ1; HRMS: calcd.
for (MþH)þ C24H26O6: 411.1808; found: 411.1789.
(R)-5,6,7,8,5’,6’,7’,8’-Octahydro-[1,1’]binaphthalenyl-
2,2’-diol (5a): Acetic acid (145 mL) was added to a 500 mL
flask charged with (R)-BINOL (5.18 g, 18.1 mmol) and
Adamꢀs catalyst (PtO2 ·H2O, 0.52 g, 2.1 mmol). The atmos-
phere of the flask was purged under vacuum and flushed with
H2 three times. The reaction was stirred under a balloon pres-
sure H2 atmosphere for 36 h. The reaction mixture was filtered
through a bed of Celite, diluted with CHCl3 (250 mL), and
washed with excess water. The organic layer was washed with
a saturated aqueous NaHCO3 solution (500 mL), and dried
over Na2SO4. Concentration of the organic layer yielded (R)-
5,6,7,8,5’,6’,7’,8’-octahydro-[1,1’]binaphthalenyl-2,2’-diol as a
white solid; yield: 5.18 g (17.6 mmol, 97%). Characterization
and spectroscopic data was in agreement with lit. values.[22]
(R)-2,2’-Dimethoxy-5,6,7,8,5’,6’,7’,8’-octahydro-[1,1’]bi-
naphthalenyl (13): A solution of (R)-5,6,7,8,5’,6’,7’,8’-octahy-
dro-[1,1’]binaphthalenyl-2,2’-diol (1.47 g, 5.00 mmol) in DMF
(16 mL) was added dropwise via cannula to a 100 mL flask
charged with NaH (60% w/w in oil, 840 mg, 35.0 mmol) in
DMF (14 mL) at 08C. The mixture was stirred at 08C for
40 min. Methyl iodide (2.84 g, 20.0 mmol) was added dropwise
via syringe at08C and the mixture was stirred at 08C for 20 min.
The solution was removed from the ice bath and allowed to
warm to room temperature over 1.5 h. The mixture was placed
in a 08C bath, and the reaction was quenched with the careful
addition of water. The white precipitate was filtered, dissolved
in CHCl3 (30 mL), and washed with excess water. The organic
layer was dried over Na2SO4. Concentration of the organic lay-
er afforded (R)-2,2’-dimethoxy-5,6,7,8,5’,6’,7’,8’-octahydro-
1
[a]2D1: ꢀ223.08 (c 0.98, CHCl3); H NMR (400 MHz, CDCl3):
d¼7.60–7.75 (m, 12H), 7.40–7.50 (m, 4H), 7.30–7.38 (m,
2H), 7.21 (s, 2H), 3.28 (s, 2H), 2.84 (t, J¼6.0 Hz, 4H), 2.50–
2.60 (m, 2H), 2.20–2.30 (m, 2H), 1.66–1.83 (m, 8H);
13C NMR (75.0 MHz, CDCl3): d¼152.8, 140.8, 139.3, 138.4,
135.9, 132.7, 131.4, 131.1, 130.7, 129.3, 128.7, 127.1, 126.9,
126.8, 60.4, 29.4, 27.6, 23.1; IR (thin film). n¼3009, 2934,
2858, 2837, 1488, 1461, 1387, 1289, 1254, 1240, 1217, 1075,
1034, 1020, 842, 760, 698, 666 cmꢀ1; HRMS: calcd. for (Mþ
H)þ C46H43O2: 627.3263; found: 627.3202.
Procedure 2: (R)-3,3’-Bis-(3,5-dimethylphenyl)-2,2’-di-
methoxy-5,6,7,8,5’,6’,7’,8’-octahydro-[1,1’]binaphthalenyl
(10b): Glyme (5 mL) was added to a flask charged with
Pd(PPh3)4 (35 mg, 0.03 mmol) and (R)-3,3’-dibromo-2,2’-di-
methoxy-5,6,7,8,5’,6’,7’,8’-octahydro-[1,1’]binaphthalenyl (480
mg, 1.0 mmol) under an argon atmosphere. The mixture was
stirred 10 min at room temperature. The boronic acid
(450 mg, 3.0 mmol) was added to the flasks a solution in
EtOH (5 mL). 2.0 mL of a 2.0 M aqueous Na2CO3 solution
(4.0 mmol) were added. The mixture was refluxed at 908C
for 18 h. The reaction mixture was allowed to cool to room tem-
perature, and filtered through a bed of Celite with EtOAc
washings. The EtOAc washings were washed with a saturated
aqueous NaCl solution, dried over Na2SO4, and concentrated.
Theresidue wassubjectedto flash chromatography onsilica gel
and eluted with hexane and benzene (1:1) to afford (R)-3,3’-
bis-(3,5-dimethylphenyl)-2,2’-dimethoxy-5,6,7,8,5’,6’,7’,8’-oc-
tahydro-[1,1’]binaphthalenyl as a white foam; yield: 520 mg
(0.97 mmol, 97%).
[1,1’]binaphthalenyl as
a white powder; yield: 1.55 g
(4.80 mmol, 96%). Characterization and spectroscopic data
was in agreement with lit. values.[20]
(R)-3,3’-Dibromo-2,2’-dimethoxy-5,6,7,8,5’,6’,7’,8’-octa-
hydro-[1,1’]binaphthalenyl (9): Bromine (3.00 g, 18.7 mmol)
was added dropwise to a 250 mL flask charged with (R)-2,2’
-dimethoxy-5,6,7,8,5’,6’,7’,8’-octahydro-[1,1’]binaphthalenyl
(2.7 g, 8.3 mmol) in CH2Cl2 (85 mL) at ꢀ308C. The solution
was stirred at ꢀ308C for 25 min. 70 mL of a saturated aqueous
NaHSO3 solution were added, and the mixture was allowed to
warm to room temperature over 1 h. The reaction mixture was
diluted with CH2Cl2 and water. The organic layer was washed
with a saturated aqueous NaHCO3 solution, and dried over
Representative Procedures for the Demethylation of
10a – e to Yield Compounds 8a – e
(R)-3,3’-Bis-biphenyl-4-yl-5,6,7,8,5’,6’,7’,8’-octahydro-
[1,1’]binaphthalenyl-2,2’-diol
(8d):
BBr3
(530 mg,
1238
ꢁ 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
Adv. Synth. Catal. 2004, 346, 1231–1240