2,2′-Dimethoxy-1,1′-binaphthyl-3,3′-diboronic acid, a versatile intermediate in the synthesis of 3,3′-diaryl substituted binaphthyl derivatives

Article abstract of DOI:10.1007/PL00010145

2,2′-Dimethoxy-1,1′-binaphthyl-3,3′-diboronic acid was prepared in 48% yield from 2,2′-dimethoxy-1,1′-binaphthyl and used as a key intermediate in Suzuki cross-coupling reactions to yield various 2,2′,3,3′-symmetrically substituted binaphthyl derivatives

Full text of DOI:10.1007/PL00010145

Monatshefte fuÈr Chemie 129, 1319±1327 (1998)
2,20-Dimethoxy-1,10-binaphthyl-3,30-diboronic
Acid, a Versatile Intermediate in the Synthesis
of 3,30-Diaryl Substituted Binaphthyl
Derivatives
Ã
Petra Kratky, Ulrike Haslinger, and Michael Widhalm
È
Institut fuÈr Organische Chemie, Universitat Wien, A-1090 Wien, Austria
Summary. 2,20-Dimethoxy-1,10-binaphthyl-3,30-diboronic acid was prepared in 48% yield from
2,20-dimethoxy-1,10-binaphthyl and used as a key intermediate in Suzuki cross-coupling reactions to
yield various 2,20,3,30-symmetrically substituted binaphthyl derivatives in 22±72% yield.
Keywords. Cross-coupling reaction; ortho-Lithiation.
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2,2 -Dimethoxy-1,1 -binaphthyl-3,3 -diborsaure, ein vielseitiges Zwischenprodukt in der
Synthese 3,30-diarylsubstituierter Binaphthylderivate
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Zusammenfassung. 2,2 -Dimethoxy-1,1 -binaphthyl-3,3 -diborsaure wurde in 48% Ausbeute aus
2,20-Dimethoxy-1,10-binaphthyl hergestellt und als SchluÈsselverbindung in Suzuki-Cross-Kupplungs-
reaktionen eingesetzt, um zahlreiche 2,20,3,30 symmetrisch tetrasubstituierte Binaphthylderivate
darzustellen.
Introduction
3,30-Disubstituted 2,20-binaphthol derivatives have attracted much attention as
chiral modi®ers in Lewis acid catalyzed reactions [1]. Whereas the ortho lithiation/
electrophilic substitution protocol permits the introduction of various substituents
like halogens, -CHO, -COOH, -CR2OH, alkyls, or trialkylsilyl groups in a simple
one-step procedure [2], the tethering of aromatic moieties often requires a two-step
sequence. It has recently been demonstrated that 3,30-dibromo- and 3,30-diiodo-
2,2-dimethoxy-1,10-binaphthyl are suitable precursors in the Suzuki cross-coupling
reaction with aromatic boronic acids [3]. An alternative approach in this
methodology is the object of the present report.
Results and Discussion
We recently discovered an alternative approach to a group of 3,30-diarylsubstituted
binaphthyls 4a-l when exchanging -B(OH)2 and halogen functionalities in the
Ã
Corresponding author

1320
P. Kratky et al.
a
considerable amount of amide was formed
Scheme 1

2,20-Dimethoxy-1,10-binaphthyl-3,30-diboronic Acid
1321
reactants of a Suzuki coupling (Scheme 1) which offers two advantages. The key
intermediate, the 3,30-diboronic acid 2 of 2,20-dimethoxy-1,10-binaphthyl (1) was
obtained by two-fold ortho-lithiation using a standard procedure [4] which was
followed by reaction with B(OCH3)3. After extractive work-up only a single
recrystallization step was necessary to obtain a pure product, thus avoiding a
chromatographic puri®cation step. Moreover, various aromatic compounds bearing
halogen rather than boronic acid substituents are either commercially available or
easy to prepare. The convenient access of functionalized haloaromates (e.g. via
selective monolithiation of symmetrical dihalogenated species) and the mild
reaction conditions applied in the Suzuki coupling reaction result in the tolerance
for many functional groups and opens the access to more complicated structures
incorporating a C2-symmetrical binaphthyl fragment. We found this method to
proceed with acceptible yields in the majority of cases, producing binaphthyl
derivativatives 4a±l, in part with extended functionalized side arms. The ®nal
cleavage of the methoxy group proceeds smoothly under standard conditions
(BBr3/CH2Cl2, 0ꢀC) to afford the bisphenol in good yield as demonstrated for 5c,
5f, and 5j. The application of the new ligands in asymmetric Diels-Alder reactions
will be the subject of further investigations.
Experimental
Melting points: Ko¯er melting point apparatus, uncorrected. NMR: Bruker AM 400 spectrometer at
400.13 MHz (1H) and 100.61 MHz (13C) in CDCl3 if not otherwise noted; chemical shifts are
reported in ppm relative to CHCl3 (7.24 or 77.00 ppm). Coupling patterns are designated as
s(ingulett), d(oublett), t(riplett), p(seudo), and b(road). 13C{1H} NMR spectra are recorded in a J-
modulated mode (APT). MS: MAT 900 spectrometer (70 eV electron impact or ®eld desorption).
Petroleum ether (PE) and CH2Cl2 were distilled, N,N,N0,N0-tetramethylethylenediamine
(TMEDA) was distilled from CaH2, diethyl ether from LiA1H4, n-BuLi was used as a 1.6 molar
solution in hexane (Aldrich). Column chromatography was performed on silica gel Si 60, 25±40 mm
(Merck). All other chemicals were of analytical grade and used without further puri®cation.
Compounds 3a-d were commercially available and used as purchased, 2,20-dimethoxy-1,10-
binaphthyl (1) was prepared according to Ref. [4]. Elemental analyses of the new compounds agreed
satisfactorily with the calculated values.
2,20-Dimethoxy-1,10-binaphthyl-3,30-diboronic acid (2, C22H20B2O6)
To a solution of 5 ml of TMEDA (33.3 mmol) in 180 ml of dry diethyl ether, 22.5 ml of n-BuLi
(36.0 mmol) were added. After stirring for 10 min at room temp. 5.00 g of 2,20-dimethoxy-1,10-
binaphthyl (1, 15.9 mmol) was added and the suspension was stirred for 3 h. The mixture was cooled
to ꢁ78ꢀC, and 10.8 ml of B(OCH3)3 (95.1 mmol) were added slowly. After reaching room temp. the
reaction mixture was worked up extractively using 2 N HCl and CH2Cl2. The organic phase was
dried (Na2SO4) and evaporated. The solid residue was crystallized from ethyl acetate. The
crystallization process starts slowly and takes several days.
1
Yield: 3.09 g (48%); m.p.: >240ꢀC (dec.); H NMR (DMSO-d6): ꢀ ˆ 3.42 (6H, s), 6.97 (2H, d,
J ˆ 8.5 Hz), 7.25 (2H, pt, J ˆ 7.6 Hz), 7.38 (2H, pt, J ˆ 7.4 Hz), 7.97 (2H, d, J ˆ 8.1 Hz), 8.17±8.23
(4H, s, D2O-exchange), 8.20 (2H, s) ppm; 13C NMR (DMSO±d6) ꢀ ˆ 60.58 (CH3), 122.73 (C),
124.30 (CH), 125.04 (CH), 126.53 (CH), 128.19 (CH), 129.69 (C), 134.31 (C), 135.43 (CH), 158.70
‡
(C), 170.35 (C) ppm; MS (240ꢀC): m/z ˆ 402 (2%, M ).

1322
P. Kratky et al.
3-Bromo-N-methylaniline (3e)
Prepared from 3-bromoaniline in three steps following reported procedures [5].
1H NMR: ꢀ ˆ 2.80 (3H, s), 3.75 (1H, s), 6.51 (1H, ddd, J ˆ 8.2, 2.3, 0.8 Hz), 6.73 (1H, pt,
J ˆ 2.1 Hz), 6.84 (1H, ddd, J ˆ 7.8, 1.8, 0.8 Hz), 7.04 (1H, pt, J ˆ 8.0 Hz) ppm; 13C NMR: ꢀ ˆ 30.45
(CH3), 111.19 (CH), 114.75 (CH), 119.85 (CH), 123.25 (C), 130.36 (CH), 150.52 (C) ppm; MS
‡
(30ꢀC): m/z ˆ 185/187 (100/100%, M ).
4-Bromo-40-iododiphenylether (3f)
A solution of 10.00 g of bis(4-bromophenyl)ether (30.5 mmol) in 150 ml of diethylether was
degassed and cooled to ꢁ78ꢀC. 4.5 ml of TMEDA (30.0 mmol) were added followed by 20 ml of
n-BuLi (32.0 mmol). After stirring for 3 h, 11.4 g of I2 (44.9 mmol) were added, and the reaction was
allowed to reach room temp. Excess of I2 was destroyed by addition of a sat. Na2SO3 solution. The
organic layer was separated, and the aqueous layer was repeatedly extracted with ether. The
combined extracts were washed with brine and dried (Na2SO4). The solvent was evaporated, and the
crude product was recrystallized from 200 ml of CH3OH.
1
Yield: 7.59 g (66%); m.p.: 90±95ꢀC [6]; H NMR: ꢀ ˆ 6.76 (2H, d, J ˆ 8.7 Hz), 6.88 (2H, d,
J ˆ 9.0 Hz), 7.45 (2H, d, J ˆ 8.8 Hz), 7.63 (2H, d, J ˆ 9.0 Hz) ppm; 13C NMR: ꢀ ˆ 86.50 (C), 116.24
(C), 120.65 (CH), 120.92 (CH), 132.81 (CH), 138.78 (CH), 155.81 (C), 156.86 (C) ppm; MS (50ꢀC):
‡
m/z ˆ 374/376 (100/100%, M ).
Bis(4-iodophenyl)ether (3g)
A similar procedure as reported for the preparation of diiododibenzofuran was applied [7]. 34.00 g of
diphenylether (0.20 mol), 48 g of I2 (0.19 mol), and 60 ml of conc. HNO3 in 150 ml of CHCl3 were
re¯uxed for 3 h. The precipitated product was separated, washed with water and PE and dried over
KOH. Crystallization from PE/ethyl acetate (4:1) afforded 56.52 g (67%) of 3g.
M.p.: 139ꢀC [6]; 1H NMR: ꢀ ˆ 6.77 (4H, d, J ˆ 8.9 Hz), 7.63 (4H, d, J ˆ 8.9 Hz) ppm; 13C NMR:
‡
ꢀ ˆ 86.62 (C), 121.04 (CH), 138.80 (CH), 156.70 (C) ppm; MS (30ꢀC): m/z ˆ 422 (100%, M ).
4-Bromo-40-methyldiphenylether (3h)
A solution of 10.00 of bis(4-bromophenyl)ether (30.5 mmol) in 180 ml of dry ether was degassed
and cooled to ꢁ78ꢀC. 5 ml of TMEDA (33.5 mmol) and 21 ml of n-BuLi (33.5 mmol) were added
dropwise. After 3 h, 20 ml of CH3I (320 mmol) were introduced by a syringe and the reaction was
slowly warmed up to room temp. Water was added, and the mixture was extracted with ether. The
organic phase was dried and the solvent was removed under vacuum. The crude product was ®ltered
over a short pad of silica gel. The obtained product was suf®ciently pure for the next step.
Yield: 7.47g (93%) [8]; 1H NMR: ꢀ ˆ 2.34, (3H, s), 6.85 (2H, d, J ˆ 8.8 Hz), 6.90 (2H, d,
J ˆ 8.5 Hz), 7.15 (2H, d, J ˆ 8.5 Hz), 7.40 (2H, d, J ˆ 8.7 Hz) ppm; 13C NMR: ꢀ ˆ 21.14 (CH3),
115.57 (C), 119.67 (CH), 120.33 (CH), 130.81 (CH), 132.99 (CH), 133.86 (C), 154.67 (C), 157.58
‡
(C) ppm; MS (30ꢀC): m/z ˆ 262/264 (100/100%, M ).
4-Bromo-40-aminodiphenylether (3i)
Prepared according to a reported procedure [9].
1H NMR: ꢀ ˆ 3.46 (1H, bs), 6.66 (2H, m), 6.78 (2H, m), 6.83 (2H, m), 7.34 (2H, m) ppm;
13C NMR: ꢀ ˆ 114.25 (C), 116.18 (CH), 118.81 (CH), 121.08 (CH), 132.33 (CH), 143.02 (C), 148.02
‡
(C) 158.12 (C) ppm; MS (30ꢀC): m/z ˆ 263/265 (100/100%, M ).

2,20-Dimethoxy-1,10-binaphthyl-3,30-diboronic Acid
1323
1-Iododibenzofuran (3j)
Prepared according to a reported procedure [10].
1H NMR: ꢀ ˆ 7.10 (1H, pt, J ˆ 7.7 Hz), 7.36 (1H, pt, J ˆ 7.5 Hz), 7.49 (1H, pt, J ˆ 7.8 Hz), 7.66
(1H, d, J ˆ 8.3 Hz), 7.81 (1H, d, J ˆ 7.7 Hz), 7.90 (1H, d, J ˆ 7.7 Hz), 7.92 (1H, d, J ˆ 7.7 Hz) ppm;
13C NMR: ꢀ ˆ 75.86 (C), 112.48 (CH), 120.93 (CH), 121.55 (CH), 123.57 (CH), 124.80 (CH),
124.93 (C), 124.98 (C), 128.14 (CH), 136.33 (CH), 156.09 (C), 156.83 (C) ppm; MS (40ꢀC):
‡
m/z ˆ 294 (100%, M ).
3,6-Dibromodibenzofuran (3k)
Prepared from dibenzofuran [11].
1H NMR: ꢀ ˆ 7.42 (2H, d J ˆ 8.8 Hz), 7.55 (2H, dd, J ˆ 8.7, 2.0 Hz), 8.00 (2H, d, J ˆ 1.8 Hz)
ppm; 13C NMR: ꢀ ˆ 113.37 (CH), 115.94 (C), 123.69 (CH), 125.14 (C), 130.73 (CH), 155.34 (C)
‡
ppm; MS (50ꢀC): m/z ˆ 326 (100%, M ).
3-Bromo-6-trimethylsilyl-N-methylcarbazol, (6, C16H18BrNSi)
The preparation followed a standard procedure [12]. In a typical run, 4.00 g of 3,6-dibromo-N-
methylcarbazol (11.8 mmol) were converted to 6.45 g (82%) of 6.
M.p.: >54ꢀC (dec, CH2Cl2/PE); 1H NMR: ꢀ ˆ 0.35 (9H, s), 3.79 (3H, s), 7.23 (1H, d, J ˆ 8.7 Hz),
7.38 (1H, d, J ˆ 8.0 Hz), 7.53 (1H, dd, J ˆ 8.7, 1.8 Hz), 7.63 (1H, dd, J ˆ 8.2, 1.1 Hz), 8.19 (1H, d,
J ˆ 1.0 Hz), 8.23 (1H, d, J ˆ 1.8 Hz) ppm; 13C NMR: ꢀ ˆ ꢁ0.65 (CH3), 29.10 (CH3), 108.32 (CH),
109.81 (CH), 111.83 (C), 121.62 (C), 122.97 (CH), 124.43 (C), 125.64 (CH), 128.23 (CH), 129.66
‡
(C), 131.24 (CH), 139.56 (C), 141.83 (C) ppm; MS (50ꢀC): m/z ˆ 331/333 (4/5%, M ), 316/318 (8/
8%, M-CH3), 259/261(100/90%, M-Si(CH3)3); HRMS: calc. for C16H18BrNSi: 331.039, found:
331.041.
3-Iodo-6-bromo-N-methylcarbazole (3l, C13H9BrIN)
The preparation followed a standard procedure [12]. In a typical run, 6.35 g of 5 (16.4 mmol)
afforded 5.57 g (75%) of 3l.
1
M.p.: >230ꢀC (dec); H MMR: ꢀ ˆ 3.70 (3H, s), 7.09 (1H, d, J ˆ 8.4 Hz), 7.16 (1H, d, J ˆ 8.4
Hz), 7.51 (1H, dd, J ˆ 8.9, 2.0 Hz), 7.67 (1H, dd, J ˆ 8.9, 1.8 Hz), 8.02 (1H, d, J ˆ 1.5 Hz), 8.22 (1H,
d, J ˆ 2.0 Hz) ppm; 13C NMR: ꢀ ˆ 29.17 (CH3), 81.63 (C), 109.97 (CH), 110.63 (CH), 112.07 (C),
122.98 (C), 123.05 (CH), 124.01 (C), 128.94 (CH), 129.17 (CH), 134.48 (CH), 139.40 (C), 140.20
‡
(C) ppm; MS: (30ꢀC): mz ˆ 385/387 (5/5%, M ), 259/261 (100/100%, M-I); HRMS: calc. for
C13H9BrIN: 384.896, found: 384.894.
Suzuki cross-coupling (typical procedure): 3,30-Bis (4-(4-bromophenoxy)phenyl)-2,20-dimethoxy-1,
10-binaphthyl (4f)
To a degassed solution of 4.198 g of 4-bromo-40-iododiphenylether (3f, 11.2 mmol) and 150 mg of
Pd(PPh3)4 (0.13 mmol) in 150 ml of toluene, 7.46 ml of a 2 M Na2CO3 solution (14.9 mmol) and a
solution of 1.500 g of 2,20-dimethoxy-1,10-binaphthyl-3,30-diboronic acid (2, 3.7 mmol) in 9 ml of
dry ethanol were added sequentially. The reaction mixture was re¯uxed in the dark for 20 h. After
cooling, the bulk of solvent was removed under vacuum, and saturated NaCl solution was added. The
mixture was extracted exhaustively with CH2Cl2, and the combined extracts were washed with brine
and dried (Na2SO4). The solvent was removed, and the crude product was puri®ed by column
chromatography (PE/CH2Cl2, 6:4) and recrystallyzed (PE/CH2Cl2) to give 1.696 g (56%) of 4f.

1324
P. Kratky et al.
3,30-Diphenyl-2,20-dimethoxy-1,10-binaphthyl (4a ˆ 4b) [3, 4]
1NMR: ꢀ ˆ 3.19 (6H, s), 7.22±7.27 (4H, m), 7.35±7.43 (4H, m), 7.44±7.49 (4H, m), 7.78 (4H, m),
7.91 (2H, bd, J ˆ 8.4 Hz), 7.98 (2H, s) ppm; 13C NMR: ꢀ ˆ 60.52 (CH3), 124.98 (CH), 125.77 (CH),
125.89 (C), 126.25 (CH), 127.26 (CH), 128.04 (CH), 128.30 (CH), 129.31 (CH), 130.50 (CH),
130.79 (C), 133.61 (C), 135.01 (C), 138.91 (C), 154.07 (C) ppm; MS (200ꢀC): m/z ˆ 466 (100%,
‡
M ).
3,30-Bis(3-bromophenyl)-2,20-dimethoxy-1,10-binaphthyl (4c, C34H24Br2O2)
1
M.p.: 92±97ꢀC; H NMR: ꢀ ˆ 3.18 (6H, s), 7.20 (2H, bd, J ˆ 7.9 Hz), 7.28 (2H, ddd, J ˆ 7.9, 6.5,
1.0 Hz), 7.32 (2H, t, J ˆ 7.9 Hz), 7.41 (2H, ddd, J ˆ 7.9, 6.6, 1.0 Hz), 7.51 (2H, ddd, J ˆ 8.4, 2.0,
1.0 Hz), 7.70 (2H, m), 7.91 (2H, bd, J ˆ 9.8 Hz), 7.92 (2H, d, J ˆ 3.5 Hz), 7.96 (2H, s) ppm;
13C NMR: ꢀ ˆ 60.70 (CH3), 122.36 (C), 125.24 (CH), 125.69 (CH), 125.87 (C), 126.67 (CH), 128.04
(CH), 128.17 (CH), 129.83 (CH), 130.32 (CH), 130.65 (CH), 130.69 (C), 132.10 (CH), 133.50 (C),
‡
133.79 (C), 140.88 (C), 153.74 (C) ppm; MS (300ꢀC): m/z ˆ 624 (100%, M ).
3,30-Bis(2-cyanophenyl)-2,20-dimethoxy-1,10-binaphthyl (4d, C36H24N2O2)
After work-up, the crude product was dissolved in CH2Cl2 and ®ltered over silica gel. Preparative
TLC (ethyl acetate/PE 30:70) gave a crystalline product.
M.p.: >245ꢀC (dec); 1H NMR: ꢀ ˆ 3.16 (6H, s), 7.35 (4H, m), 7.43 (2H, dd, J ˆ 8.5, 3.9 Hz), 7.47
(2H, ptd, J ˆ 7.5, 1.3 Hz), 7.64 (2H, dd, J ˆ 8.1, 1.6 Hz), 7.69 (2H, ptd, J ˆ 8.1, 1.3 Hz), 7.79 (2H, dd,
J ˆ 7.8, 1.0 Hz), 7.92 (2H, d, J ˆ 8.8 Hz), 7.98 (2H, s) ppm; 13C NMR: ꢀ ˆ 60.98 (CH3), 113.19 (C),
118.46 (C), 125.09 (C), 125.42 (CH), 125.94 (CH), 127.26 (CH), 127.76 (CH), 128.24 (CH), 130.26
(C), 131.14 (CH), 131.32 (CH), 131.80 (C), 132.29 (CH), 133.00 (CH), 134.43 (C), 142.62 (C),
‡
153.59 (C) ppm; MS (280ꢀC): m/z ˆ 516 (100%, M ).
3,30-Bis(3-N-methylaminophenyl)-2,20=dimethoxy-1,10-binaphthyl (4e, C36H32N2O2)
1H NMR: ꢀ ˆ 3.15 (6H, s), 7.01 (2H, d, J ˆ 8.9 Hz), 7.21 (4H, m), 7.30 (2H, bd, J ˆ 8.4 Hz), 7.36
(4H, m), 7.75 (2H, bd, J ˆ 8.4 Hz), 7.88 (2H, bd, J ˆ 7.9 Hz), 8.02 (2H, s), 8.07 (2H, s), 8.08 (2H, s),
8.34 (2H, s) ppm; 13C NMR: ꢀ ˆ 60.44 (CH3), 110.64 (CH), 112.12 (CH), 112.16 (C), 120.98 (CH),
122.37 (C), 123.03 (CH), 125.04 (C), 125.06 (CH), 125.80 (CH), 126.00 (C), 126.13 (CH), 128.00
(CH), 128.12 (CH), 128.43 (CH), 130.39 (C), 130.70 (CH), 130.96 (C), 133.39 (C), 135.47 (C),
‡
138.31 (C), 139.14 (C), 154.17 (C) ppm; MS (200ꢀC): m/z ˆ 524 (100%, M ).
3,30-Bis(4-(4-bromophenoxy)phenyl)-2,20-dimethoxy-1,10-binaphthyl (4f, C46H32Br2O4)
M.p.: 125±130ꢀC; 1H NMR: ꢀ ˆ 3.20 (6H, s), 6.97 (4H, d, J ˆ 8.7 Hz), 7.10 (4H, d, J ˆ 8.5 Hz), 7.24
(4H, m), 7.42 (2H, t, J ˆ 8.1 Hz), 7.47 (4H, d, J ˆ 8.7 Hz), 7.76 (4H, d, J ˆ 8.5 Hz), 7.92 (2H, d,
J ˆ 8.1 Hz), 7.98 (2H, s) ppm; 13C NMRa: ꢀ ˆ 60.48 (CH3), 115.78 (C), 118.67 (CH), 120.59 (CH),
125.07 (CH), 125.72 (CH), 125.89 (C), 126.29 (CH), 127.99 (CH), 130.29 (CH), 130.79 (CH),
132.71 (CH), 133.54 (C), 134.14 (C), 134.24 (C), 153.97 (C), 156.17 (C), 156.35 (C) ppm; MS
‡
(140ꢀC): m/z ˆ 809 (10%, M ).
3,30-Bis(4-(4-iodophenoxy)phenyl)-2,20-dimethoxy-1,10-binaphthyl (4g, C46H32I2O4)
M.p.: 133±135ꢀC; 1H NMR: ꢀ ˆ 3.21 (6H, s), 6.85 (4H, d, J ˆ 8.9 Hz), 7.10 (4H, d, J ˆ 8.7 Hz), 7.25
(4H, m), 7.41 (2H, pt, J ˆ 8.0 Hz), 7.64 (4H, d, J ˆ 8.9 Hz), 7.76 (4H, d, J ˆ 8.6 Hz), 7.92 (2H, d,
a
One Cquart was not observed

2,20-Dimethoxy-1,10-binaphthyl-3,30-diboronic Acid
1325
J ˆ 8.2 Hz), 7.98 (2H, s) ppm; 13C NMRa: ꢀ ˆ 60.48 (CH3), 86.08 (C), 118.80 (CH), 121.00 (CH),
125.08 (CH), 125.74 (CH), 125.91 (C), 126.31 (CH), 128.01 (CH), 130.30 (CH), 130.81 (CH),
133.58 (C), 134.16 (C), 134.35 (C), 138.70 (CH), 154.00 (C), 156.03 (C), 157.27 (C) ppm; MS
‡
(250ꢀC): m/z ˆ 902 (10%, M ), 776 (15%, M-I), 684 (100%, M-OC6H4I).
3,30-Bis(4-(4-methylphenoxy)phenyl)-2,20-dimethoxy-1,10-binaphthyl (4h, C48H38O4)
1
M.p.: 133±140ꢀC; H NMR: ꢀ ˆ 2.34 (6H, s), 3.20 (6H, s), 6.99 (4H, d, J ˆ 8.5 Hz), 7.07 (4H, d,
J ˆ 8.6 Hz), 7.16 (4H, d, J ˆ 8.4 Hz), 7.23 (4H, m), 7.39 (2H, m), 7.72 (4H, d, J ˆ 8.6 Hz), 7.90 (2H,
d, J ˆ 8.2 Hz), 7.96 (2H, s) ppm; 13C NMR: ꢀ ˆ 20.70 (CH3), 60.43 (CH3), 118.00 (CH), 119.27
(CH), 124.98 (CH), 125.76 (CH), 125.92 (C), 126.17 (CH), 127.97 (CH), 130.21 (CH), 130.27 (CH),
130.58 (CH), 130.81 (C), 133.36 (C), 133.51 (C), 134.33 (C), 154.08 (C), 154.56 (C), 157.32 (C)
‡
ppm; MS (270ꢀC): m/z ˆ 678 (100%, M ).
3,30-Bis(4-(4-aminophenoxy)phenyl)-2,20-dimethoxy-1,10-binaphthyl (4i, C46H36N2O4)
1
M.p.: 125±129ꢀC; H NMR: ꢀ ˆ 3.19 (6H, s), 3.57 (4H, bs) 6.67 (4H, m), 6.92 (4H, m), 7.01 (4H,
m), 7.22 (4H, m), 7.37 (2H, ddd, J ˆ 8.0, 5.6, 2.3 Hz), 7.68 (4H, m), 7.88 (2H, bd, J ˆ 8.2 Hz), 7.94
(2H, s) ppm; 13C NMR: ꢀ ˆ 60.39 (CH3), 116.20 (CH), 116.89 (CH), 121.19 (CH), 124.92 (CH),
125.72 (CH), 125.86 (C), 126.08 (CH), 127.91 (CH), 130.11 (CH), 130.43 (CH), 130.77 (C), 132.58
(C), 133.42 (C), 134.42 (C), 142.79 (C), 148.36 (C), 154.05 (C), 158.36 (C) ppm; MS (280ꢀC):
‡
m/z ˆ 681 (50%, M ).
3,30-Bis(1-dibenzofuranyl)-2,20-dimethoxy-1,10-binaphthyl (4j, C46H30O4)
1
M.p.: 205±209ꢀC; H NMR: ꢀ ˆ 3.25 (6H, s), 7.30±7.52 (14H, m), 7.78 (2H, d, J ˆ 7.6 Hz), 7.96
(6H, m), 8.25 (2H, s) ppm; 13C NMR: ꢀ ˆ 60.87 (CH3), 111.81 (CH), 119.85 (CH), 120.64 (CH),
122.67 (CH), 122.75 (CH), 123.41 (C), 124.39 (C), 124.48 (C), 124.99 (CH), 125.53 (C), 125.95
(CH), 126.56 (CH), 127.08 (CH), 128.23 (CH), 128.79 (CH), 129.85 (C), 130.57 (C), 131.61 (CH),
‡
134.11 (C), 153.96 (C), 154.68 (C), 156.21 (C) ppm; MS (240ꢀC): m/z ˆ 646 (100%, M ).
3,30-Bis(6-bromo-dibenzofuran-3-yl)-2,20-dimethoxy-1,10-binaphthyl (4k, C46H28Br2O4)
1
M.p.: 135±139ꢀC; H NMR: ꢀ ˆ 3.20 (6H, s), 7.30 (4H, m), 7.44 (2H, m), 7.45 (2H, d, J ˆ 6.8 Hz),
7.55 (2H, dd, J ˆ 8.1, 1.5 Hz), 7.65 (2H, d, J ˆ 8.1 Hz), 7.92 (2H, dd, J ˆ 8.9, 1.9 Hz), 7.95 (2H, d,
J ˆ 8.1 Hz), 8.06 (2H, s), 8.12 (2H, d, J ˆ 1.7 Hz), 8.33 (2H, d, J ˆ 1.4 Hz) ppm; 13C NMR: ꢀ ˆ 60.58
(CH3), 111.63 (CH), 113.24 (CH), 115.67 (C), 121.56 (CH), 123.38 (C), 123.70 (CH), 125.20 (CH),
125.80 (CH), 126.05 (C), 126.36 (C), 126.43 (CH), 128.08 (CH), 129.57 (CH), 129.98 (CH), 130.78
(CH), 130.87 (C), 133.66 (C), 134.06 (C), 134.63 (C), 154.01 (C), 155.32 (C), 156.10 (C) ppm; MS
‡
(280ꢀC): m/z ˆ 802 (5%, M ), 636 (22%), 560 (78%).
3,30-Bis(6-Bromo-N-methylcarbazo-3-yl)-2,20-dimethoxy-1,10-binaphthyl (4l, C48H34Br2N2O2)
M.p.: 320±325ꢀC (dec); 1H NMR : ꢀ ˆ 3.23 (6H, s), 3.88 (6H, s), 7.25±7.34 (6H, m), 7.44 (2H, m),
7.49 (2H, d, J ˆ 8.9 Hz), 7.67 (2H, bd, J ˆ 8.4 Hz), 7.97 (4H, m), 8.10 (2H, s), 8.28 (2H, bs), 8.48
(2H, s) ppm; 13C NMR: ꢀ ˆ 29.31 (CH3), 60.43 (CH3), 108.48 (CH), 109.99 (CH), 111.83 (C),
121.18 (CH), 121.92 (C), 123.19 (CH), 124.67 (C), 124.98 (CH), 125.86 (CH), 126.05 (CH), 126.10
a
One Cquart was not observed

1326
P. Kratky et al.
(C), 127.96 (CH), 128.21 (CH), 128.38 (CH), 130.22 (C), 130.56 (CH), 130.99 (C), 133.46 (C),
‡
135.43 (C), 139.95 (C), 140.67 (C), 154.28 (C) ppm; MS (290ꢀC): m/z ˆ 830 (100%, M ).
3,30-Bis(3-bromophenyl)-2,20-dihydroxy-1,10-binaphthyl (5c, C32H20Br2O2) (typical procedure)
A solution of 300 mg of 4c (0.48 mmol) in 8 ml of CH2Cl2 was cooled to ꢁ78ꢀC and, 0.15 ml of
BBr3 (excess) were added. The solution was stirred ®rst at ꢁ78ꢀC (0.5 h) and then at room temp.
(5 h). Water was added to the ice cold solution, and the aqueous layer was extracted twice with
CH2Cl2 (2Â10 ml). The organic extracts were washed with brine and dried (Na2SO4). Evaporation
left a white powder which was dried in vacuo at 80ꢀC overnight;
1
Yield: 286 mg (100%); m.p.: 106±109ꢀC; H NMR: ꢀ ˆ 5.30 (2H, s), 7.19 (2h, bd, J ˆ 8.5 Hz),
7.33 (4H, m), 7.40 (2H, m), 7.52 (2H, m), 7.66 (2H, m), 7.89 (2H, pt, J ˆ 1.8 Hz), 7.92 (2H, bd,
J ˆ 7.5 Hz), 8.01 (2H, s) ppm; 13C NMR: ꢀ ˆ 112.06 (C), 122.41 (C), 124.12 (CH), 124.64 (CH),
127.84 (CH), 128.24 (CH), 128.61 (CH), 129.20 (C), 129.41 (C), 129.84 (CH), 130.68 (CH), 131.73
(CH), 132.59 (CH), 133.03 (C), 139.53 (C), 150.01 (C) ppm; MS (FD, 190ꢀC): m/z ˆ 596.2
‡
(100%, M ); HRMS: calc. for C32H20Br2O2: 593.9830, found: 593.9841.
3,30-Bis(4-(4-bromophenoxy)phenyl)-2,20-dihydroxy-1,10-binaphthyl (5f C44H28Br2O4)
1
Yield: 93%; m.p.: 176±179ꢀC; H NMR: ꢀ ˆ 5.33 (2H, s), 6.95 (4H, bd, J ˆ 8.8 Hz), 7.09 (4H, bd,
J ˆ 8.8 Hz), 7.20 (2H, bd, J ˆ 8.3 Hz), 7.31 (2H, bpt, Jꢂ7.3 Hz), 7.38 (2H, bpt, Jꢂ7.2 Hz), 7.44 (4H,
bd, J ˆ 8.8 Hz), 7.70 (4H, bd, J ˆ 8.8 Hz), 7.91 (2H, bd, J ˆ 7.8 Hz), 8.01 (2H, s) ppm; 13C NMRa
ꢀ ˆ 112.18 (C), 115.94 (C), 118.70 (CH), 120.76 (CH), 124.19 (CH), 124.47 (CH), 127.45 (CH),
128.44 (CH), 129.50 (C), 129.86 (C), 131.16 (CH), 131.35 (CH), 132.76 (CH), 132.81 (C), 150.18
‡
(C), 156.27 (C), 156.58 (C) ppm; MS (255ꢀC): m/z ˆ 780 (100%, M ), 610/608 (95/80%); HRMS:
calc. for C44H28Br2O4: 788.0354, found: 778.0392.
3,30-Bis(1-dibenzofuranyl)-2,20-dihydroxy-1,10-binaphthyl (5j, C44H26O4)
Chromatography on SiO2 (CH2Cl2/PE, 1:1) afforded at white foam. Yield: 69%; 1H NMR: ꢀ ˆ 5.54
(2H, s), 7.35 (2H, ddd, J ˆ 8.0, 7.5, 0.9 Hz), 7.39±7.49 (10H, m), 7.52 (2H, bd, J ˆ 8.2 Hz),
7.74±7.76 (2H, m), 7.96±8.02 (6H, m), 8.28 (2H, s) ppm; 13C NMR: ꢀ ˆ 111.86 (CH), 112.79 (C),
120.32 (CH), 120.70 (CH), 122.07 (C), 122.78 (CH), 122.85 (CH), 124.29 (C), 124.33 (CH), 124.55
(CH), 124.67 (C), 127.22 (CH), 127.55 (CH), 128.63 (CH), 128.84 (CH), 129.06 (C), 129.31 (C),
132.56 (CH), 133.37 (C), 150.58 (C), 153.95 (C), 156.13 (C) ppm; MS (150ꢀC): m/z ˆ 618.9 (100%,
‡
M ); HRMS: calc. for C44H26O4: 618.183, found: 618.186.
References
[1] See: (a) Narasaka K (1991) Synthesis 1; (b) Altenbach HJ (1992) In: Organic Synthetic
Highlights 1991. VCH, p 66; (c) Maruoka K, Yamamoto H (1993) In: Ojima I (ed) Asymmetric
Synthesis. VCH, p 413
[2] Snieckus V (1990) Chem Rev 90: 879
[3] Cox P J, Wang W, Snieckus V (1992) Tetrahedron Lett 33: 2253
[4] Lingenfelter DS, Helgeson RC, Cram DJ (1981) J Org Chem 46: 393
[5] Gorvin JH (1955) J Chem Soc 83
[6] Scarborough HA (1929) J Chem Soc London 2361
a
One Cquart was not observed

2,20-Dimethoxy-1,10-binaphthyl-3,30-diboronic Acid
1327
[7] Gilman H, Brown GE, Bywater WG, Kirkpatrick WH (1934) J Am Chem Soc 56: 2473
[8] Brewster RQ, Slocombe R (1945) J Am Chem Soc 67: 562
[9] Suter CM (1929) J Am Chem Soc 51: 258
[10] Gilman H, Avakian S (1945) J Am Chem Soc 67: 349
[11] (a) Hoffmeister W (1871) Ann Chem Pharm 159: 191; (b) Cullinane NM, Davey HG, Pad®eld
HJH (1934) J Chem Soc 716
[12] Paek K, Kim K, Kim Y (1993) Bull Korean Chem Soc 14: 732
Received August 3, 1998. Accepted August 24, 1998