Synthesis of (±) binaphthols via oxidative coupling of naphthols by cerium ammonium nitrate (CAN)

Article abstract of DOI:10.1081/SCC-100000189

2-Naphthol and methyl 3-hydroxy-2-naphthoate were oxidized to give the corresponding (±) binaphthols by cerium ammonium nitrate (CAN) in good yields.

Full text of DOI:10.1081/SCC-100000189

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SYNTHESIS OF (±) BINAPHTHOLS VIA OXIDATIVE
COUPLING OF NAPHTHOLS BY CERIUM AMMONIUM
NITRATE (CAN)
Peng Jiang a & Shijie Lu b
a State Key Laboratory for Oxo Synthesis and Selective Oxidation , The Chinese Academy
of Science , Lanzhou Institute of Chemical Physics , Lanzhou, 730000, China
b State Key Laboratory for Oxo Synthesis and Selective Oxidation , The Chinese Academy
of Science , Lanzhou Institute of Chemical Physics , Lanzhou, 730000, China
Published online: 09 Nov 2006.
To cite this article: Peng Jiang & Shijie Lu (2001) SYNTHESIS OF (±) BINAPHTHOLS VIA OXIDATIVE COUPLING OF
NAPHTHOLS BY CERIUM AMMONIUM NITRATE (CAN), Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 31:1, 131-134, DOI: 10.1081/SCC-100000189
To link to this article: http://dx.doi.org/10.1081/SCC-100000189
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SYNTHETIC COMMUNICATIONS, 31(1), 131–134 (2001)
SYNTHESIS OF ( ) BINAPHTHOLS
VIA OXIDATIVE COUPLING
OF NAPHTHOLS BY CERIUM
AMMONIUM NITRATE (CAN)
Peng Jiang and Shijie Lu∗
State Key Laboratory for Oxo Synthesis and Selective
Oxidation, Lanzhou Institute of Chemical Physics,
The Chinese Academy of Science,
Lanzhou 730000, China
ABSTRACT
2-Naphthol and methyl 3-hydroxy-2-naphthoate were oxi-
dized to give the corresponding ( ) binaphthols by cerium ammo-
nium nitrate (CAN) in good yields.
Chiral binaphthol derivatives have been extensively used in stereoselective
synthesis (1). Resolution of ( ) binaphthols is a common method for obtaining
this chiral reagent (2). ( ) Binaphthols have been synthsized by direct oxidative
coupling of 2-naphthols using Fe (III) (3), Mn (III) (4–6), and Cu (II) (7) salts. We
report herein that cerium ammonium nitrate (CAN) is also an effective oxidative
coupling reagent for 2-naphthols (Scheme 1).
It was found that CAN can oxidize 2-naphthols (1a, 2a) to give ( ) binaph-
thols (1b, 2b) in high yield (∼90%) quickly at room temperature in either MeOH
or acetonitrile (Table 1).
∗ To whom correspondence should be addressed.
131
Copyright ꢀ 2001 by Marcel Dekker, Inc.
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C

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JIANG AND LU
Scheme 1.
It should be pointed out that CAN is a less suitable oxidation reagent for the
cross-coupling reaction of 2-naphthol with methyl 3-hydroxy-2-naphthoate. A 1:1
mixture (3a) gave only 47% of the cross-coupling oxidative product 3b, together
with the coupling products 1b (22%) and 2b (25%). The statistical distribution of
the products in the reaction of 2-naphthol with methyl 3-hydroxy-2-naphthoate (the
approximate molar ratio of 1b:2b:3b is 1:1:2) suggests that the oxidative coupling
reaction of 2-naphthols by CAN may proceed via a free-radical mechanism as
shown in Scheme 2.
EXPERIMENTAL
Melting points were uncorrected. 1HNMR spectra were recorded at a Bruker
AM 400 spectrometer in CDCl3 using TMS as internal standard. IR spectra were
obtainedusingKBrpelletsonaNicolet10DXFT-IRspectrophotometer. Analytical
Table 1. Yield of Coupling Products of 2-Naphthols
Yielda
(%)
M.P
(◦C)
Temp
(◦C)
Time
(min)
Substrate
Solvent
MeOH
Acetonitrile
MeOH
Acetonitrile
MeOH
Product
1a
1a
2a
2a
3a
1b
1b
2b
2b
3b
92
89
94
90
47
215
216
234
234
182
r. t
r. t
r. t
r. t
r. t
10
10
15
15
10
aIsolated yield.

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( ) BINAPHTHOLS
133
Scheme 2.
thin layer chromatography (TLC) was performed on silica gel (precoated silica gel
plate F254, Merck) and visualized with a UV lamp.
General Procedure
2-Naphthol (1a, 0.38 g, 2.5 mmol) was dissolved in 20 mL of MeOH at
room temperature. Nitrogen was bubbled through the solution, into which CAN
(1.39 g, 2.53 mmol) in 15 mL of MeOH was added with stirring until the mixture
turned reddish. The mixture was evaporated in vacuo and the residue was poured
into 100 mL of H2O at 0◦C and filtered. The crude product was purified by silica
gel chromatography using a petroleum ether-diethyl ether (3:1, v:v) as eluant.
Analytical Data for the Products
1b:whitecrystallinesolid. M.p:215◦C(lit. (9):214–217◦C). IR(KBr, cm−1):
ν = 3404, 3485. 1HNMR (CDCl3, ppm): δ = 7.25 (m, 10H, arom.), 7.93 (m, 2H,
arom.), 10.54 (s, 2H, -OH).
2b: yellow crystalline solid. M.p: 234◦C. IR (KBr, cm−1): ν = 3202, 3437.
1HNMR (CDCl3, ppm): δ = 4.05 (s, 6H, COOCH3), 7.19–7.39 (m, 6H, arom.),
7.85 (m, 2H, arom.), 8.67 (s, 2H, arom.), 10.66 (s, 2H, -OH). Anal. calc. For
C24H18O6: C 71.54, H 4.45. Found C 71.62, H 4.51.
3b: yellowish crystalline solid. M.p: 181◦C (lit. (7): 182–183◦C). IR (KBr,
cm−1): ν = 3258, 3433. 1HNMR (CDCl3, ppm): δ= 4.08 (s, 3H, COOCH3), 4.99
(s, 1H, -OH), 7.25–7.40 (m, 7H, arom.), 7.87–7.99 (m, 3H, arom.), 8.78 (s, 1H,
arom.), 10.81 (s, 1H, -OH).
REFERENCES
1. Rossini, C.; Franzini, L.; Raffaeli, A.; Salvadori, P. Synthesis 1991, 503.
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JIANG AND LU
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Received March 27, 2000

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