Iron-Promoted Domino Dehydrogenative Annulation of Deoxybenzoins and Alkynes Leading to β-Aryl-α-Naphthols

Article abstract of DOI:10.1002/adsc.202000625

A strategy for synthesis of β-aryl-α-naphthols has been established through an iron-promoted domino C(sp³)?H/C(sp)?H and C(sp²)?H/C(sp)?H dehydrogenative coupling of deoxybenzoins and alkynes. The synthesis uses inexpensive materials

Full text of DOI:10.1002/adsc.202000625

Title: Iron-Promoted Domino Dehydrogenative Annulation of
Deoxybenzoins and Alkynes Leading to β-Aryl-α-Naphthols
Authors: Xue-Qing Zhu, Rui-Li Guo, Xing-Long Zhang, Ya-Ru Gao,
Qiong Jia, and Yong-Qiang Wang
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000625
Link to VoR: https://doi.org/10.1002/adsc.202000625

10.1002/adsc.202000625
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Iron-Promoted Domino Dehydrogenative Annulation of
Deoxybenzoins and Alkynes Leading to -Aryl--Naphthols
Xue-Qing Zhu a, Rui-Li Guo a, Xing-Long Zhang a, Ya-Ru Gao a, Qiong Jia a*, and
Yong-Qiang Wang a*
a
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, School of Foreign
Languages, College of Chemistry & Materials Science, Northwest University, Xi’an 710069, People’s Republic of
China.
Tel.: 86-029-81535025
Fax: 86-029-81535025
E-mail: wangyq@nwu.edu.cn, jiaqiong@nwu.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.
Abstract: A strategy for synthesis of -aryl--naphthols has naphthols and the synthetic protocol should have potential
been established through an iron-promoted domino C(sp3)– applications in medicinal, materials science, and related
H/C(sp)–H and C(sp2)–H/C(sp)–H dehydrogenative coupling areas.
of deoxybenzoins and alkynes. The synthesis uses
inexpensive materials with a broad substrate scope and
features simple operations with excellent regioselectivity.
This study provides an alternative access to various -aryl-
Keywords: -Aryl--naphthols; Iron-promoted; C-H
functionalization; Deoxybenzoins; Radical reactions
Introduction
-Aryl--naphthol structural motif is embedded in
numerous natural and bioactive molecules
(Figure1).[1] These molecules have shown a wide
range of pharmacological activities including anti-
HIV, anti-viral, antitumor, and
anticancer
properties.[2] In addition to their interesting
pharmacological activities, these molecules also
possess
remarkable
electrochemical
and
photochemical properties and can be used as valuable
synthetic intermediates for functional materials.[3]
Naphthol-derived axially chiral compounds are
widely used as chiral ligands in metal complexes and
catalysts.[4] Suzuki-type cross-coupling reaction
between -naphthols and aryl partners is the typical
method for the preparation of -aryl--naphthols
(Scheme 1a).[5] However, this method requires use of
a multistep process and/or starting materials which
are difficult to access. Recently, several groups[6a–f]
reported efficient syntheses of highly substituted
Scheme 1.The synthesis of -aryl--naphthols.
-naphthol via an elegant direct intermolecular C–H
functionalization process (Scheme 1b). Although the
method is concise and powerful, the protocol requires
use of substrates possessing an active methylene
group or its variant. Indeed, we could well repeat
Narender’s results[6c] with ethyl benzoylacetate and
phenylacetylene (2a) as the substrates, but the
reaction of deoxybenzoin (1a) with phenylacetylene
under the same conditions did not give the desired -
phenyl--naphthol
product,
indicating
that
deoxybenzoins are the challenging substrates for the
reaction (Scheme 1c). We were attracted by the
Figure 1. The compounds containing -aryl--naphthol.
1
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10.1002/adsc.202000625
Advanced Synthesis & Catalysis
efficiency in transforming deoxybenzoins and
arylacetylenes into -aryl--naphthols in terms of
atom- and step-economy, and environmentally benign
profiles and were motivated to explore the essential
reaction conditions.
combination (entries 11 and 12).
A
control
experiment showed that, in the absence of Fe2O3, the
product 3a could not be detected under otherwise
identical conditions (entry 13). Finally, in the absence
of the iron catalyst, other oxidants failed to promote
this transformation. K2S2O8 (1.00 equiv) and DDQ
(1.00 equiv) only provided 11% and 9% yields,
respectively; and PhI(OAc)2 (1.00 equiv) did not
generate 3a (entry 14).
At present, while the precious metal catalysts
(especially platinum-group metals: Ru, Rh, Pd etc.)
are ubiquitous in laboratory and industry applications,
there is a growing impetus to replace them with much
more sustainable and earth-abundant metals.[7] This is
due to not only the scarce and expensive nature of the
precious metals, but also their relatively high
toxicity.[8] Among the earth-abundant metals, iron is
particularly attractive because it is the second most
abundant metal on earth and is one of the cheapest of
all metals. Moreover, iron is closely related to the life
and plays a very important role in the human body as
a “king metal”.[9] Recently, the iron-catalyzed organic
transformations have received great attentions.[10]
Despite considerable progresses have been made in
the field, iron catalysis is still in its infancy. Herein,
we report on an iron-promoted domino
dehydrogenative annulation of deoxybenzoins with
alkynes to form -aryl--naphthols. To the best of
our knowledge, this is the first report that allows the
synthesis of various -aryl--naphthols in an
effective and concise manner by direct intermolecular
dehydrogenation annulation of deoxybenzoins and
alkynes.
Table 1. Optimization of conditions for the synthesis of -
aryl--naphthol 3a.[a]
[Fe]
Yield
(%)[b]
15
Entry
Temp. Sol-
(ºC)
Atmo-
sphere
vent
(equiv)
1[c]
2[c]
3[c]
4[d]
5[e]
6[f]
7
FeSO4 (0.15) 135
FeCl3 (0.15) 135
Fe2O3 (0.15) 135
Fe2O3 (0.15) 135
Fe2O3 (0.15) 135
Fe2O3 (0.15) 135
Fe2O3 (1.00) 135
Fe2O3 (1.00) 135
Fe2O3 (1.00) 135
xylene
xylene
xylene
xylene
xylene
xylene
xylene
xylene
xylene
xylene
air
air
air
air
air
air
air
O2
Ar
Ar
5
53
51
62
<50
65
40
8
82
9
10[g]
Results and Discussion
Other irons
(1.00)
135
<55
Our investigation started with a reaction between
deoxybenzoin (1a) and phenylacetylene (2a) in
xylene with 15 mol % of iron species as the catalyst
and potassium persulfate (K2S2O8) as the oxidant at
135 ºC in air. To our delight, the desired product 3a
was obtained with the catalyst FeSO4, FeCl3 or Fe2O3
(Table 1, entries 1–3) with Fe2O3 affording the best
result. Then, using Fe2O3 as the catalyst, other
oxidants were examined. Na2S2O8 provided a slightly
low yield (51%, entry 4), while 2,3-dichloro-5,6-
dicyano-1,4-benzoquinone (DDQ) gave a better yield
(62%, entry 5). Other oxidants, such as tert-butyl
hydroperoxide,[11] hydrogen peroxide (30 wt.% in
water), dicumyl peroxide, di-tert-butyl peroxide,[12] 2-
iodoxybenzoic acid, and PhI(OAc)2, provided less
than 50% yields (entry 6). Considering that Fe2O3 can
also act as the oxidant and is much cheaper than
DDQ, 1.00 equiv of Fe2O3 was used along without
adding another oxidant. It is pleased to observe an
improved yield of 3a to 65% (entry 7). Next, the
reaction was investigated under different atmospheres.
It was demonstrated that oxygen was inferior to the
reaction, whereas argon atmosphere provided the best
yield (82%, entry 8 vs. entry 9). Use of other iron
species including a variety of Fe2+ and Fe3+ salts
instead of Fe2O3 led to decreased yields or no
formation of the desired product 3a (entry 10).
Optimization on reaction temperatures and solvents
indicated that 135 ºC and xylene remained the best
11[g]
12[g]
13
Fe2O3 (1.00) others xylene
Ar
Ar
Ar
Ar
<76
<47
0
Fe2O3 (1.00) others others
–
–
135
135
xylene
xylene
14[h]
<12
[a] Reaction conditions: unless otherwise noted, the reaction
was carried out with 1a (0.5 mmol) and 2a (1.0 mmol) in
solvent (3 mL) under Ar (1 atm) atmosphere at 135 ºC for
[b]
[c]
20 h.
Isolated yields.
Using K2S2O8 (1.00 equiv) as
the oxidant. [d] Using Na2S2O8 (1.00 equiv) as the oxidant.
[e]
[f]
Using DDQ (1.00 equiv) as the oxidant. Using other
oxidant: tert-butyl hydroperoxide (1.00 equiv, 21% yield),
hydrogen peroxide (30 wt. % in water, 1.00 equiv, 16%
yield), dicumyl peroxide (1.00 equiv, 41% yield), di-tert-
butyl peroxide (1.00 equiv, 49% yield), 2-iodoxybenzoic
acid (1.00 equiv, 17% yield), and PhI(OAc)2 (1.00 equiv,
[g]
[h]
37% yield)
See the Supporting Information.
In the
absence of iron catalyst, K2S2O8 (1.00 equiv) and DDQ
(1.00 equiv) provided 11% and 9% yields, respectively,
and PhI(OAc)2 (1.00 equiv) did not provide 3a.
Having established the optimal reaction conditions,
we next examined the substrate scope and generality
of the iron-promoted dehydrogenative annulation.
Deoxybenzoins (1) bearing either an electron-
donating or electron-withdrawing group on both
aromatic rings all reacted smoothly with the alkyne
2
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10.1002/adsc.202000625
Advanced Synthesis & Catalysis
reaction to afford the desired benzothiophene,
benzofuran, and indole products 3z–3cc in 46–77%
yields, respectively. Similarly, the substrates 1 with a
heteroaromatic ring on the other side, such as indole
and thiophene rings, reacted smoothly with 2a, to
afford the corresponding products 3dd and 3ee in
75% and 78% yields, respectively. It should be
mentioned that the phenyl group of phenylacetylene
(2a) was only found at the C4 position of -naphthols,
and no 3-phenyl isomers could be detected in the
reaction mixtures. The results indicated that the
annulation reaction features excellent regioselectivity.
-Ketoester (e.g. ethyl benzoylacetate) is an enabling
substrate in many organic reactions, but it could not
react with 2a to generate the corresponding -
hydroxy--naphthoate under the current reaction
conditions. It suggests that our annulation protocol
has remarkable selectivity for deoxybenzoin
substrates.
Then, we applied the iron-promoted annulation
using a series of aryl-substituted alkynes. As
illustrated in Scheme 3, both electron-donating (Me,
OMe) and electron-withdrawing (NO2, F and Cl)
substituents were well tolerated on the phenyl ring of
2 to furnish the products 4a–4l. 2-Ethynylpyridine,
which contains a heterocycle moiety, was compatible
with the reaction conditions to afford the product 4m
in 63% yield. Again the reaction showed excellent
regioselectivity with the aryl group of arylacetylenes
Scheme 2. Substrate scope of deoxybenzoins. The reaction
was carried out with 1 (0.5 mmol), 2a (1.0 mmol) and
Fe2O3 (0.5 mmol) in xylene (3 mL) under Ar (1 atm)
atmosphere at 135 ºC for 20 h. Isolated yields are given.
attached to the C4-position of -naphthols. The
structure of 4h was confirmed by single crystal X-ray
structural analysis (see the Supporting Information).
2a to afford the desired -aryl--naphthols (3) in
good yields (Scheme 2). Various functional groups,
such as fluoro, chloro, bromo, methyl, methoxy,
phenyl, and nitro groups were tolerated under the
conditions, which provided great opportunities for
further functionalization of the compounds 3b–3v.
Tolerance of the C–Br bond under the annulation
conditions is remarkably valuable due to many
opportunities for synthetic manipulation of the C–Br
bond under mild conditions. It is found that the
deoxybenzoin with meta-substitute on the left
aromatic ring reacted with 2a successfully to afford
the annulated product 3p, while the ortho-substituted
analogue didn’t react with 2a, presumably caused by
a steric effect. The anthracene and binaphthyl
compounds 3w–3y could be obtained in 72–77%
yield, implying that the extended ring systems on
both reaction partners did not exert visible influence
on the annulation. The synthesized binaphthyls are
found in many axial chiral catalysts (e.g. vanols),[13]
and the current synthetic method should have broad
applications in the catalysis area. Heteroarenes are
prevalent in many biologically relevant molecules.
Gratifyingly, the substrates with heteroaromatic rings
on the left side of 1, such as thiophene, furan, and
pyrrole rings, were also suitable for the annulation
Scheme 3. Substrate scope of arylacetylenes. Reaction
conditions: 1 (0.5 mmol), 2 (1.0 mmol) and Fe2O3 (0.5
mmol) in xylene (3 mL) under Ar (1 atm) atmosphere at
135 ºC for 20 h. Isolated yields are given.
Next, methyl propiolate (5, R3 = H), a non-aryl-
substituted alkyne, was examined for the annulation
(Scheme 4). It was pleased to find that methyl
propiolate was also suitable for the iron-promoted
3
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10.1002/adsc.202000625
Advanced Synthesis & Catalysis
annulation with various deoxybenzoins to provide the
desired -aryl--naphthols 6a–6f in 70–79% yields.
The excellent regioselectivity was observed, namely,
the methoxycarbonyl group was found at the C4-
position of the -naphthols and the C3-substituted
isomers were not detected. The structure of the
products 6a and 6b were unambiguously confirmed
by single crystal X-ray diffraction analysis (see the
Supporting Information). Finally, two internal
alkynes were investigated for the annulation. Methyl
phenylpropiolate (5g, R3 = Ph) and dimethyl
acetylenedicarboxylate (5h, R3 = CO2Me) reacted
with 1a successfully to give the corresponding
products 6g and 6h in 43% and 73% yields,
respectively. Excellent regioselectivity was also
observed for the formation of 6g from the
unsymmetrical alkyne. In the previous reports,[14] the
reaction of 1-phenylpropan-2-one and 2a could
produce the naphthalene product. However, we did
not detect any similar naphthalene derivative under
our annulation conditions.
implemented under the above standard reaction
conditions. Without the alkyne 2a, 1a reacted with
TEMPO to afford 7a in 72% yield (Eq. 2). In the
absence of both the alkyne 2a and TEMPO, the
homocoupling dimer 8 of 1a was obtained in 42%
yield (Eq. 3). These results further demonstrated that
the benzyl radical was very likely involved in the
iron-promoted annulation reaction. Finally, the
ketone 9 was used to react with 2a under the standard
reaction conditions, but the annulation product 10
was not generated at all (Eq. 4). A competitive
reaction of 1a and 9 with the alkyne 2a was carried
out (Eq. 5). Interestingly, it only afforded 3a in 76%
yield, but 10 was not detected. This finding indicated
that the current annulation protocol has good
preference for the reaction of deoxybenzoins. In order
to identify the origin of the C3-hydrogen atom of -
aryl--naphthols, an experiment using the deuterium-
labeled D-2a was carried out (Eq. 6). The reaction of
1a with deuterated phenylacetylene D-2a proceeded
smoothly under the standard reaction conditions to
give the corresponding D-3a in 71% yield with the
deuterium totally incorporated into the C3-position.
The results implied that the C3-H of -aryl--
naphthols came from the terminal alkynes which
should engage in an addition reaction in the
annulation process.
Scheme 4. Annulation of propiolates. The reaction was
carried out with 1 (0.5 mmol), 5 (1.0 mmol) and Fe2O3 (0.5
mmol) in xylene (3 mL) under Ar (1 atm) atmosphere at
135 ºC for 20 h. Isolated yields are given.
To understand the mechanism of the reaction, we
carried out a series of control experiments. First,
under the standard reaction conditions, 2,2,6,6-
tetramethylpiperidinooxy (TEMPO, 3.0 equiv) was
introduced into the reaction system of 1a and 2a.
After 20 hours at 135 ºC, instead of 3a, the adduct 7a
formed from 1a and TEMPO was isolated in 41%
yield along with recovery of 1a (48%) and 2a (96%)
(Eq. 1). The results indicated that the benzoyl-
stabilized benzyl radical should be formed in the
reaction. Then, additional control experiments were
On the basis of the above results and the related
reports in the literature,[15] a tentative reaction
mechanism for the iron-promoted dehydrogenative
annulation of deoxybenzoins with alkynes to form -
4
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10.1002/adsc.202000625
Advanced Synthesis & Catalysis
aryl--naphthols is proposed in Scheme 5. Initially,
Fe3+ oxidizes the substrate 1a to generate the
stabilized radical A,[16] which subsequently undergoes
a regioselective addition reaction to the alkyne 2a to
form the vinyl radical B. The observed
regioselectivity of the addition might be attributed to
the stabilization of the vinyl radical by the ajacent
aryl group.[17] Intramolecular cyclization of B
produces the cyclic radial intermediate C, which
might be converted into D by Fe3+ oxidation and
deprotonation. Finally, keto–enol tautomerism
transforms D into the desired product 3a. In the
reaction, argon atmosphere was found superior than
air and oxygen presumably due to the inhibition of
the radical reaction by molecular oxygen.[18]
NMR) spectra and carbon-13 nuclear magnetic resonance
(13C NMR) spectra were recorded on Bruker
Inova-400 (400 MHz) spectrometer (1H and 13C NMR at
1
400 and 100 MHz, respectively). H and 13C NMR spectra
1
were recorded in CDCl3 (TMS,  = 0.00 ppm for H and 
= 77.10 ppm for 13C) or DMSO-d6 ( = 2.50 ppm for 1H
and  = 39.52 ppm for 13C) using the solvent residue peaks
as the internal references. Multiplicities are reported as
follows: s = singlet, d = doublet, t = triplet, m = multiplet,
br. s = broad singlet. Infrared (IR) data were recorded
using film on potassium bromide plate on a Bruker Tensor
27 FT-IR spectrometer. Absorbance frequencies are
reported in reciprocal centimeters (cm–1). High resolution
mass spectra were acquired on a Bruker Daltonics
MicroTof-QII mass spectrometer. X-ray single crystal
structural analyses were performed on Bruker Smart
APEXIICCD instrument using Mo-Kα radiation. The
structures were solved and refined using the SHELXTL
software package.
General procedure for -Aryl--Naphthols: A 10 mL
round-bottom
flask
was
charged
with
2-
phenylacetophenone derivatives (0.5 mmol), Fe2O3 (0.5
mmol) and xylene (3 mL). Then, the flask was degassed
for 50 seconds, and then was filled with argon gas. After
alkyne derivative (1.0 mmol) was added, the resultant
mixture was stirred at 135 ºC for 20 h under argon. The
reaction mixture was cooled to room temperature and was
filtered off through a small pad of silica gel with rinsing by
EtOAc. The combined filtrate was concentrated under
reduced pressure and the residue was then purified by flash
column chromatography over silica gel to afford the
desired product.
Scheme 5. Proposed annulation mechanism.
Conclusion
In summary, we have developed a novel approach for
the synthesis of -aryl--naphthols through an iron-
promoted
domino
C(sp3)−H/C(sp)−H
and
2,4-Diphenylnaphthalen-1-ol (3a):[19] 121.4 mg, 82%
yield; White solid; mp = 103–104 ºC; Eluant: EtOAc–
C(sp2)−H/C(sp)−H dehydrogenative couplings of
deoxybenzoins and alkynes. The new strategy
features inexpensive materials and simple reaction
conditions, excellent functional group tolerance, good
substrate scope, and excellent regioselectivity. The
described protocol should have general applications
in the synthesis of various bioactive and functional -
aryl--naphthols. Preliminary mechanistic studies
indicate that the annulation proceeds via a radical
process. Further transformations of -aryl--
naphthols are currently underway and the results will
be reported in due course.
1
petroleum ether (1:20, Rf = 0.30). H NMR (400 MHz,
DMSO-d6)  9.44 (s, 1H), 8.42 (d, J = 8.3 Hz, 1H), 7.81 (d,
J = 8.3 Hz, 1H), 7.68 (d, J = 7.5 Hz, 2H), 7.56–7.56 (m,
1H), 7.51–7.39 (m, 8H), 7.37–7.31 (m, 2H); 13C NMR
(100 MHz, DMSO-d6)  148.6, 140.1, 138.7, 131.8, 131.3,
130.0 (× 2), 129.7 (× 2), 129.5, 128.5 (× 2), 128.3 (× 2),
127.1, 126.8, 126.5, 126.3, 125.3, 125.2, 123.0, 122.9; IR
(film): 3502, 3051, 3024, 2922, 2852, 1630, 1572, 1496,
1412, 1367, 1049, 1022, 758, 702 cm–1; HRMS (ESI) m/z
calculated for C22H15O- [M–H]-: 295.1128; found 295.1130.
2-(2-Bromophenyl)-4-phenylnaphthalen-1-ol (3b): 142.1
mg, 76% yield; White solid; mp = 67–68 ºC; Eluant:
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
1
Experimental Section
MHz, DMSO-d6)  9.43 (s, 1H), 8.39 (d, J = 8.0 Hz, 1H),
7.84 (d, J = 8.0 Hz, 1H), 7.74 (d, J = 8.0 Hz, 1H), 7.61–
7.38 (m, 9H), 7.36–7.29 (m, 1H), 7.11 (s, 1H); 13C NMR
(100 MHz, DMSO-d6)  148.9, 139.9, 139.4, 132.6, 132.6,
131.6, 130.6, 129.9 (× 2), 129.6, 129.3, 128.5 (× 2), 127.6,
127.0, 126.7, 125.7, 125.2, 125.2, 124.1, 123.1, 122.1; IR
(film): 3523, 3055, 2922, 2852, 1572, 1448, 1371, 1209,
1024, 858, 756, 698 cm-1; HRMS (ESI) m/z calculated for
C22H14BrO- [M-H]-: 373.0234; found 373.0237.
General information: All reactions were carried out under
argon. Unless otherwise noted, all commercial reagents
and solvents were used as received without further
purification. Most of reagents bought from Adamas-beta.
Analytical thin-layer chromatography was performed with
0.25 mm pre-coated commercial silica gel plates (TLC
Silica Gel 60 F254), visualization of the developed
chromatogram was performed by fluorescence. Flash
column chromatography was performed over silica gel
(200–300 mesh). Proton nuclear magnetic resonance (1H
5
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10.1002/adsc.202000625
Advanced Synthesis & Catalysis
2-(3-Bromophenyl)-4-phenylnaphthalen-1-ol (3c): 145.8
mg, 78% yield; White solid; mp = 69–70 oC; Eluant:
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
131.6, 131.6 (d, JCF = 8.0 Hz, × 2), 131.2, 130.0 (× 2),
129.5, 128.5 (× 2), 127.4, 127.0, 124.5, 124.2, 123.0, 121.1,
115.1 (d, JCF = 21.0 Hz, × 2), 21.6; IR (film): 3427, 2924,
2854, 1660, 1601, 1508, 1446, 1228, 1157, 833, 771, 700
cm-1; HRMS (ESI) m/z calculated for C23H16FO- [M-H]-:
327.1191; found 327.1190.
1
MHz, DMSO-d6)  9.63 (s, 1H), 8.44 (d, J = 8.4 Hz, 1H),
7.90 (s, 1H), 7.81 (d, J = 8.3 Hz, 1H), 7.66 (d, J = 7.6 Hz,
1H), 7.59–7.44 (m, 7H), 7.39 (t, J = 7.6 Hz, 2H), 7.33 (s,
1H); 13C NMR (100 MHz, DMSO-d6)  148.9, 141.1,
139.9, 132.3, 131. 9, 131.6, 130.4, 130.0 (× 2), 129.5,
128.9, 128.7, 128.4 (× 2), 127.1, 126.7, 126.2, 125.4, 125.3,
123.0, 121.6, 121.4; IR (film): 3545, 3060, 2925, 1718,
1660, 1577, 1450, 1373, 1211, 1049, 883, 768, 702 cm-1;
HRMS (ESI) m/z calculated for C22H14BrO- [M-H]-:
373.0234; found 373.0235.
2-(4-Chlorophenyl)-6-methyl-4-phenylnaphthalen-1-ol
(3h): 141.1 mg, 82% yield; White solid; mp = 125–126 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  9.49 (s, 1H), 8.32 (d, J = 8.6 Hz,
1H), 7.67 (d, J = 8.2 Hz, 2H), 7.57 (s, 1H), 7.47 (d, J = 5.3
Hz, 6H), 7.39 (d, J = 8.3 Hz, 2H), 7.26 (s, 1H), 2.38 (s,
3H); 13C NMR (100 MHz, DMSO-d6)  148.8, 140.2,
137.6, 135.9, 131.8, 131.4 (× 2), 131.4, 131.3, 130.0 (× 2),
129.2, 128.5 (× 2), 128.2 (× 2), 127.5, 127.0, 124.5, 124.2,
123.1, 120.8, 21.6; IR (film): 3562, 3413, 2922, 2852,
1603, 1572, 1489, 1381, 1163, 1082, 891, 831, 767, 700
cm-1; HRMS (ESI) m/z calculated for C23H16ClO- [M-H]-:
343.0895; found 343.0903.
2-(4-Bromophenyl)-4-phenylnaphthalen-1-ol (3d): 153.3
mg, 82% yield; White solid; mp = 88–89 ºC; Eluant:
1
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
MHz, DMSO-d6)  9.57 (s, 1H), 8.41 (d, J = 8.4 Hz, 1H),
7.80 (d, J = 8.3 Hz, 1H), 7.63 (s, 4H), 7.60–7.46 (m, 6H),
7.45–7.38 (m, 1H), 7.30 (s, 1H); 13C NMR (100 MHz,
DMSO-d6)  148.8, 140.0, 137.9, 131.8 (× 3), 131.5, 131.2
(2C), 130.0 (× 2), 128.9, 128.5 (× 2), 127.1, 126.7, 126.2,
125.4, 125.3, 123.0, 121.6, 120.1; IR (film): 3541, 3458,
3064, 3021, 2925, 2854, 1660, 1595, 1489, 1365, 1217,
829, 758, 702 cm-1; HRMS (ESI) m/z calculated for
C22H14BrO- [M-H]-: 373.0234; found 373.0240.
2-(4-Methoxyphenyl)-6-methyl-4-phenylnaphthalen-1-
ol (3i): 129.2 mg, 76% yield; White solid; mp = 86–87 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  9.23 (s, 1H), 8.32 (d, J = 8.6 Hz,
1H), 7.67–7.53 (m, 3H), 7.48 (d, J = 4.3 Hz, 4H), 7.44–
7.34 (m, 2H), 7.27 (s, 1H), 7.01 (d, J = 8.6 Hz, 2H), 3.79 (s,
3H), 2.38 (s, 3H); 13C NMR (100 MHz, DMSO-d6)  158.2,
148.4, 140.4, 135.3, 131.3, 131.1, 130.9, 130.7 (× 2), 129.9
(× 2), 129.6, 128.4 (× 2), 127.2, 126.9, 124.5, 124.1, 122.9,
121.8, 113.8 (× 2), 55.1, 21.5; IR (film): 3442, 2924, 2848,
1662, 1603, 1508, 1444, 1243, 1107, 1022, 827, 762, 698
2-(4-Nitrophenyl)-4-phenylnaphthalen-1-ol (3e): 127.9
mg, 75% yield; Yellow solid; mp = 172–173 ºC; Eluant:
1
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
MHz, DMSO-d6)  9.88 (s, 1H), 8.44 (d, J = 8.3 Hz, 1H),
8.30 (d, J = 8.6 Hz, 2H), 7.98 (d, J = 8.6 Hz, 2H), 7.81 (d,
J = 8.3 Hz, 1H), 7.65–7.48 (m, 6H), 7.44 (dd, J = 8.7, 4.4
Hz, 1H), 7.38 (s, 1H); 13C NMR (100 MHz, DMSO-d6) 
149.5, 145.9, 145.9, 139.8, 132.2, 132.0, 130.9 (× 2), 130.0
(× 2), 128.6, 128.5 (× 2), 127.2 (× 2), 126.2, 125.6, 125.4,
123.4 (× 2), 123.2, 120.8; IR (film): 3425, 2922, 2850,
1595, 1516, 1344, 1205, 1103, 1047, 849, 769, 694 cm-1;
-
cm-1; HRMS (ESI) m/z calculated for C24H19O2 [M-H]-:
339.1391; found 339.1399.
6-Methoxy-2,4-diphenylnaphthalen-1-ol (3j): 130.4 mg,
80% yield; White solid; mp = 79–80 ºC; Eluant: EtOAc–
1
petroleum ether (1:20, Rf = 0.30). H NMR (400 MHz,
-
HRMS (ESI) m/z calculated for C22H14NO3 [M-H]-:
DMSO-d6)  9.36 (s, 1H), 8.35 (d, J = 9.2 Hz, 1H), 7.66 (d,
J = 8.0 Hz, 2H), 7.57–7.37 (m, 7H), 7.36–7.28 (m, 2H),
7.26–7.17 (m, 2H), 3.72 (s, 3H); 13C NMR (100 MHz,
DMSO-d6)  157.7, 148.9, 140.4, 138.8, 132.7, 130.7,
130.3, 129.8 (× 2), 129.6 (× 2), 128.6 (× 2), 128.3 (× 2),
127.0, 126.6, 124.9, 121.5, 121.1, 116.9, 104.2, 54.9; IR
(film): 3419, 2924, 2854, 1658, 1589, 1508, 1448, 1227,
1157, 1078, 835, 771, 700 cm-1; HRMS (ESI) m/z
340.0979; found 340.0984.
6-Methyl-2,4-diphenylnaphthalen-1-ol (3f): 130.2 mg,
84% yield; White solid; mp = 82–83 ºC; Eluant: EtOAc–
1
petroleum ether (1:20, Rf = 0.30). H NMR (400 MHz,
DMSO-d6)  9.36 (s, 1H), 8.32 (d, J = 8.6 Hz, 1H), 7.67 (d,
J = 7.2 Hz, 2H), 7.58 (s, 1H), 7.52–7.37 (m, 8H), 7.33 (t, J
= 7.4 Hz, 1H), 7.28 (s, 1H), 2.39 (s, 3H); 13C NMR (100
MHz, DMSO-d6)  148.7, 140.3, 138.8, 135.6, 131.6,
131.7, 129.9 (× 2), 129.7 (× 2), 129.6, 128.5 (× 2), 128.3
(× 2), 127.3, 126.9, 126.7, 124.5, 124.1, 123.0, 122.1, 21.5;
IR (film): 3423, 3026, 2922, 1657, 1601, 1493, 1444, 1238,
1028, 758, 696 cm-1; HRMS (ESI) m/z calculated for
C23H17O- [M-H]-: 309.1285; found 309.1292.
-
calculated for C23H17O2 [M-H]-: 325.1234; found
325.1226.
2-(4-Fluorophenyl)-6-methoxy-4-phenylnaphthalen-1-ol
(3k): 135.9 mg, 79% yield; White solid; mp = 82–83 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  9.38 (s, 1H), 8.33 (d, J = 9.2 Hz,
1H), 7.68 (dd, J = 8.3, 5.8 Hz, 2H), 7.58–7.44 (m, 4H),
7.40 (t, J = 6.9 Hz, 1H), 7.28–7.22 (m, 4H), 7.18 (d, J =
2.1 Hz, 1H), 3.72 (s, 3H); 13C NMR (100 MHz, DMSO-d6)
 161.1 (d, JCF = 242.0 Hz), 157.7, 148.8, 140.3, 135.0 (d,
JCF = 3.0 Hz), 132.7, 131.5 (d, JCF = 8.0 Hz, × 2), 130.6,
130.1, 129.8 (× 2), 128.5 (× 2), 127.0, 124.9, 121.4, 120.1,
116.9, 115.0 (d, JCF = 20.0 Hz, × 2), 104.2, 54.9; IR (film):
3421, 2925, 2850, 1658, 1599, 1508, 1446, 1238, 1159,
2-(4-Fuorophenyl)-6-methyl-4-phenylnaphthalen-1-ol
(3g): 136.2 mg, 83% yield; White solid; mp = 80–81 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  9.41 (s, 1H), 8.32 (d, J = 8.6 Hz,
1H), 7.68 (dd, J = 9.1, 4.6 Hz, 2H), 7.58 (s, 1H), 7.47 (s,
4H), 7.39 (d, J = 8.3 Hz, 2H), 7.26 (t, J = 8.7 Hz, 3H), 2.38
(s, 3H); 13C NMR (100 MHz, DMSO-d6)  161.2 (d, JCF
242.0 Hz), 148.7, 140.3, 135.7, 135.1 (d, JCF = 3.0 Hz),
=
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000625
Advanced Synthesis & Catalysis
1022, 835, 771, 700 cm-1; HRMS (ESI) m/z calculated for
compounds are inseparable): 94.5 mg, 61% yield
(o:p=1:1); Colorless gum; Eluant: EtOAc–petroleum ether
(1:20, Rf = 0.30). 1H NMR (400 MHz, CDCl3)  8.39 (d, J
= 8.3 Hz, 1H), 8.22 (s, 1H), 7.87 (d, J = 8.5 Hz, 1H), 7.70–
7.23 (m, 25H), 5.94 (s, 1H), 5.90 (s, 1H), 2.62 (s, 3H), 2.11
(s, 3H); 13C NMR (100 MHz, CDCl3)  147.7, 146.9, 144.9,
140.8, 137.4, 137.4, 135.3, 133.0, 131.5, 132.8, 130.8,
130.4, 130.3(× 2), 130.0 (× 3), 129.7 (× 2), 129.4, 129.4,
129.4, 128.9, 128.3 (× 2), 128.2, 128.0 (× 2), 127.6, 126.9,
126.6, 126.6, 125.8, 125.8, 125.6, 125.4, 125.3, 124.7,
124.7, 121.7 (× 2), 121.3, 120.9, 119.9, 25.2, 21.9; IR
(film): 3531, 3452, 3055, 2923, 1652, 1592, 1497, 1434,
1365, 1302, 1206, 1163, 1049, 766, 702 cm-1; HRMS (ESI)
m/z calculated for C23H17O- [M-H]-: 309.1285; found
309.1273.
-
C23H16FO2 [M-H]-: 343.1140; found 343.1148.
6-Methoxy-4-phenyl-2-(p-tolyl)naphthalen-1-ol
(3l):
136.1 mg, 80% yield; White solid; mp = 83–84 ºC; Eluant:
1
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
MHz, DMSO-d6)  9.26 (s, 1H), 8.33 (d, J = 9.2 Hz, 1H),
7.67–7.46 (m, 6H), 7.41 (d, J = 6.8 Hz, 1H), 7.30–7.20 (m,
4H), 7.18 (s, 1H), 3.72 (s, 3H), 2.34 (s, 3H); 13C NMR
(100 MHz, DMSO-d6)  157.6, 148.6, 140.4, 135.8, 135.6,
132.5, 130.5, 130.2, 129.8 (× 2), 129.4 (× 2), 128.9 (× 2),
128.5 (× 2), 126.9, 124.9, 121.5, 120.9, 116.8, 104.2, 54.9,
20.8; IR (film): 3423, 2924, 1657, 1597, 1442, 1242, 1184,
1107, 1024, 820, 768, 702 cm-1; HRMS (ESI) m/z
calculated for C24H19O2 [M-H]-: 339.1391; found 339.1394.
6-Fluoro-2,4-diphenylnaphthalen-1-ol (3q): 124.1 mg,
79% yield; White solid; mp = 73–74 ºC; Eluant: EtOAc–
petroleum ether (1:20, Rf = 0.30). H NMR (400 MHz,
DMSO-d6)  9.60 (s, 1H), 8.54–8.44 (m, 1H), 7.66 (d, J =
7.6 Hz, 2H), 7.56–7.31 (m, 11H).; 13C NMR (100 MHz,
DMSO-d6)  160.6 (d, JCF = 243.0 Hz), 148.9, 139.6, 138.4,
132.4 (d, JCF = 4.0 Hz), 131.2 (d, JCF = 5.0 Hz), 130.9,
129.8 (× 2), 129.6 (× 2), 128.6 (× 2), 128.4 (× 2), 127.3,
2-([1,1'-Biphenyl]-4-yl)-6-methoxy-4-
phenylnaphthalen-1-ol (3m): 142.8 mg, 71% yield; White
solid; mp = 167–168 ºC; Eluant: EtOAc–petroleum ether
(1:20, Rf = 0.30). 1H NMR (400 MHz, DMSO-d6)  9.43 (s,
1H), 8.34 (d, J = 9.2 Hz, 1H), 7.81–7.69 (m, 6H), 7.56–
7.47 (m, 6H), 7.44–7.34 (m, 2H), 7.34 (s, 1H), 7.24 (dd, J
= 9.2, 2.4 Hz, 1H), 7.19 (d, J = 2.4 Hz, 1H), 3.73 (s, 3H);
13C NMR (100 MHz, DMSO-d6)  157.7, 149.1, 140.4,
140.0, 138.3, 137.9, 132. 8, 130.7, 130.2 (× 3), 129.9 (× 2),
129.1 (× 3), 128.6 (× 2), 127.4, 127.1, 126.6 (× 3), 125.0,
121.6, 120.6, 117.0, 104.2, 54.9; IR (film): 3454, 2922,
2852, 1618, 1483, 1425, 1163, 1020, 901, 839, 768, 698
1
126.9, 126.4 (d, JCF = 9.0 Hz), 123.6, 122.6, 115.1 (d, JCF
=
25.0 Hz), 108.4 (d, JCF = 22.0 Hz); IR (film): 3545, 3057,
1693, 1628, 1572, 1493, 1302, 1174, 1045, 899, 816, 771,
702 cm-1; HRMS (ESI) m/z calculated for C22H14FO- [M-
H]-: 313.1034; found 313.1032.
cm-1; HRMS (ESI) m/z calculated for C29H21O2 [M-H]-:
-
401.1547; found 401.1536.
6-Chloro-2,4-diphenylnaphthalen-1-ol (3r): 132.0 mg,
80% yield; White solid; mp = 91–92 ºC; Eluant: EtOAc–
petroleum ether (1:20, Rf = 0.30). H NMR (400 MHz,
2-(3-Bromophenyl)-6-methoxy-4-phenylnaphthalen-1-
ol (3n): 155.6 mg, 77% yield; White solid; mp = 91–92 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  9.56 (s, 1H), 8.34 (d, J = 9.2 Hz,
1H), 7.88 (s, 1H), 7.65 (d, J = 7.8 Hz, 1H), 7.57–7.45 (m,
5H), 7.40 (dt, J = 12.6, 4.7 Hz, 2H), 7.29 (s, 1H), 7.24 (dd,
J = 9.2, 2.4 Hz, 1H), 7.19 (d, J = 2.3 Hz, 1H), 3.72 (s, 3H);
13C NMR (100 MHz, DMSO-d6)  157.9, 149.1, 141.2,
140.2, 133.0, 132.2, 130.8, 130.4, 129.8 (× 2), 129.8, 129.3,
128.6, 128.5 (× 2), 127.0, 124.9, 121.5, 121.4, 119.6, 117.1,
104.3, 54.9; IR (film): 3375, 2922, 2854, 1581, 1435, 1302,
1176, 1022, 827, 700 cm-1; HRMS (ESI) m/z calculated for
1
DMSO-d6)  9.64 (s, 1H), 8.42 (d, J = 9.1 Hz, 1H), 7.71 (d,
J = 1.9 Hz, 1H), 7.67 (d, J = 7.5 Hz, 2H), 7.57 (dd, J = 9.1,
2.0 Hz, 1H), 7.55–7.42 (m, 7H), 7.39–7.32 (m, 2H); 13C
NMR (100 MHz, CDCl3)  147.5, 139.9, 136.8, 133.0,
132.9, 132.2, 130.2 (× 2), 129.8, 129.8 (× 2), 129.3 (× 2),
128.6 (× 2), 128.3, 127.4, 126.4, 124.7, 124.7, 122.9,
121.2; IR (film): 3517, 2922, 2852, 1647, 1566, 1489,
1444, 1296, 1198, 1024, 874, 820, 702 cm-1; HRMS (ESI)
m/z calculated for C22H14ClO- [M-H]-: 329.0739; found
329.0740.
-
C23H16BrO2 [M-H]-: 403.0339; found 403.0348.
6-Chloro-2-(4-chlorophenyl)-4-phenylnaphthalen-1-ol
(3s): 143.4 mg, 79% yield; White solid; mp = 93–94 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  9.77 (s, 1H), 8.42 (d, J = 9.1 Hz,
1H), 7.72 (d, J = 1.9 Hz, 1H), 7.67 (d, J = 8.5 Hz, 2H),
7.56 (dd, J = 9.1, 2.0 Hz, 1H), 7.52–7.40 (m, 7H), 7.36 (s,
1H); 13C NMR (100 MHz, DMSO-d6)  149.0, 139.3,
137.1, 132.3, 131.8, 131.6, 131.5 (× 2), 131.1, 130.5, 129.9
(× 2), 128.7 (× 2), 128.3 (× 2), 127.4, 125.8, 125.7, 124.7,
123.8, 122.3; IR (film): 3519, 2924, 2854, 1655, 1568,
1487, 1369, 1294, 1196, 1084, 876, 769, 700 cm-1; HRMS
(ESI) m/z calculated for C22H13Cl2O- [M-H]-: 363.0349;
found 363.0353.
6-Methoxy-2-(2-methoxyphenyl)-4-phenylnaphthalen-
1-ol (3o): 122.8 mg, 69% yield; White solid; mp = 87–88
1
ºC; Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). H
NMR (400 MHz, CDCl3)  8.39 (d, J = 9.2 Hz, 1H), 7.54
(d, J = 7.1 Hz, 2H), 7.47 (t, J = 7.5 Hz, 3H), 7.42–7.35 (m,
2H), 7.33 (s, 1H), 7.23 (d, J = 3.5 Hz, 1H), 7.21–7.07 (m,
3H), 6.95 (s, 1H), 3.95 (s, 3H), 3.78 (s, 3H); 13C NMR
(100 MHz, CDCl3)  158.4, 155.5, 149.1, 141.1, 133.7,
132.9, 131.9, 130.9, 130.2 (× 2), 129.0, 128.4 (× 2), 127.5,
126.9, 125.2, 122.5, 121.2, 117.4, 117.1, 111.9, 104.5, 56.5,
55.3; IR (film): 3361, 2935, 1624, 1601, 1574, 1493, 1462,
1423, 1265, 1233, 1195, 1127, 1025, 907, 755 cm-1;
-
HRMS (ESI) m/z calculated for C24H19O3 [M-H]-:
355.1340; found 355.1325.
6-Bromo-2,4-diphenylnaphthalen-1-ol (3t): 144.0 mg,
77% yield; White solid; mp = 70–71 ºC; Eluant: EtOAc–
petroleum ether (1:20, Rf = 0.30). H NMR (400 MHz,
1
5-Methyl-2,4-diphenylnaphthalen-1-ol (3p-o) and 7-
methyl-2,4-diphenylnaphthalen-1-ol (3p -p) (The two
DMSO-d6)  9.64 (s, 1H), 8.34 (d, J = 9.0 Hz, 1H), 7.88 (s,
7
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000625
Advanced Synthesis & Catalysis
1H), 7.73–7.64 (m, 3H), 7.54–7.44 (m, 7H), 7.40–7.32 (m,
2H); 13C NMR (100 MHz, DMSO-d6)  148.9, 139.4,
138.2, 132.5, 130.9, 130.8, 129.9 (× 2), 129.6 (× 2), 128.7
(2C), 128.4 (× 2), 128.2, 127.4, 127.0, 126.9, 125.7, 124.9,
123.7, 120.2; IR (film): 3514, 3448, 2922, 2852, 1658,
1581, 1442, 1298, 1203, 1074, 1024, 862, 702, 698 cm-1;
HRMS (ESI) m/z calculated for C22H14BrO- [M-H]-:
373.0234; found 373.0229.
104.7, 55.3; IR (film): 3530, 3056, 2926, 2852, 1661, 1626,
1600, 1494, 1440, 1423, 1372, 1301, 1264, 1234,1034, 781
-
cm-1; HRMS (ESI) m/z calculated for C27H19O2 [M-H]-:
375.1391; found 375.1382.
6-Methoxy-4-phenyl-[2,2'-binaphthalen]-1-ol
(3y):
144.7 mg, 77% yield; White solid; mp = 75–76 ºC; Eluant:
1
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
MHz, DMSO-d6)  9.46 (s, 1H), 8.38 (d, J = 9.2 Hz, 1H),
8.18 (s, 1H), 8.03–7.91 (m, 3H), 7.86 (dd, J = 8.5, 1.6 Hz,
1H), 7.59–7.55 (m, 2H), 7.54–7.49 (m, 4H), 7.45–7.39 (m,
2H), 7.26 (dd, J = 9.2, 2.5 Hz, 1H), 7.21 (d, J = 2.4 Hz,
1H), 3.74 (s, 3H); 13C NMR (100 MHz, DMSO-d6)  158.2,
149.5, 140.8, 136.8, 133.7, 133.2, 132.3, 131.1, 130.8,
130.2 (× 2), 128.9 (× 2), 128.6, 128.4 (× 2), 127.8 (× 2),
127.4, 126.4, 126.2, 125.4, 121.9, 121.3, 117.4, 104.7,
55.3; IR (film): 3531, 2927, 2852, 1624, 1597, 1505, 1442,
1421, 1266, 1237, 1202, 1182, 1029, 823, 766, 751, 708
6-Bromo-2-(4-fluorophenyl)-4-phenylnaphthalen-1-ol
(3u): 145.0 mg, 74% yield; White solid; mp = 76–77 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  9.69 (s, 1H), 8.33 (d, J = 9.0 Hz,
1H), 7.87 (d, J = 1.8 Hz, 1H), 7.76–7.65 (m, 3H), 7.54–
7.44 (m, 5H), 7.36 (s, 1H), 7.28 (t, J = 8.8 Hz, 2H); 13C
NMR (100 MHz, DMSO-d6)  161.4 (d, JCF = 243.0 Hz),
148.9, 139.3, 134.5 (d, JCF = 3.0 Hz), 132.6, 131.6 (d, JCF
8.0 Hz, × 2), 130.9, 130.7, 129.9 (× 2), 128.7 (× 2), 128.2,
127.4, 127.0, 125.7, 124.9, 122.7, 120.3, 115.2 (d, JCF
=
-
cm-1; HRMS (ESI) m/z calculated for C27H19O2 [M-H]-:
=
375.1391; found 375.1377.
20.0 Hz, × 2); IR (film): 3419, 3067, 2922, 2858, 2351,
1660, 1590, 1506, 1227, 1156, 1086, 876, 831, 699 cm-1;
HRMS (ESI) m/z calculated for C22H13BrFO- [M-H]-:
391.0139; found 391.0148.
2-Methyl-4,6-diphenylbenzo[b]thiophen-7-ol (3z): 121.6
mg, 77% yield; Yellow solid; mp = 87–88 ºC; Eluant:
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
1
6-Bromo-2-(4-bromophenyl)-4-phenylnaphthalen-1-ol
(3v): 271.1 mg, 75% yield; White solid; mp = 83–84 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  9.73 (s, 1H), 8.34 (d, J = 9.0 Hz,
1H), 7.87 (d, J = 1.3 Hz, 1H), 7.73–7.58 (m, 5H), 7.56–
7.40 (m, 5H), 7.35 (s, 1H); 13C NMR (100 MHz, DMSO-
d6)  148.9, 139.2, 137.4, 132.7, 131.7 (× 2), 131.2 (× 2),
130.9, 130.3, 129.9 (× 2), 128.6 (× 2), 128.2, 127.4, 126.9,
125.7, 124.9, 122.4, 120.4, 120.4; IR (film): 3425, 2925,
2854, 1655, 1597, 1493, 1446, 1242, 1101, 760, 700 cm-1;
HRMS (ESI) m/z calculated for C22H13Br2O- [M-H]-:
450.9339; found 450.9336.
MHz, CDCl3)  7.59–7.49 (m, 6H), 7.43 (dt, J = 6.8, 4.5
Hz, 3H), 7.36 (t, J = 7.4 Hz, 1H), 7.24 (d, J = 3.8 Hz, 1H),
7.13 (d, J = 0.9 Hz, 1H), 5.72 (s, 1H), 2.60 (s, 3H); 13C
NMR (100 MHz, CDCl3)  145.9, 142.2, 140.9, 140.1,
136.9, 129.9, 129.7 (× 2), 129.3 (× 2), 129.1 (× 2), 128.5
(× 2), 127.9, 127.6, 127.4, 126.9, 121.6, 121.5, 16.5; IR
(film): 3399, 3057, 3025, 2920, 1732, 1665, 1598, 1466,
1437, 1386, 1220, 848, 767, 702 cm-1; HRMS (ESI) m/z
calculated for C21H15OS [M-H]-: 315.0849; found
315.0858.
2-Bromo-4,6-diphenylbenzo[b]thiophen-7-ol
(3aa):
129.2 mg, 68% yield; Yellow solid; mp = 59–60 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  9.87 (s, 1H), 7.64 (d, J = 7.5 Hz,
2H), 7.57 (d, J = 7.4 Hz, 2H), 7.53–7.43 (m, 5H), 7.39 (dd,
J = 14.6, 7.3 Hz, 2H), 7.27 (s, 1H); 13C NMR (100 MHz,
DMSO-d6)  146.6, 139.6, 137.7, 137.7, 131.8, 129.5 (× 2),
129.0, 128.8 (× 2), 128.7 (× 2), 128.7, 128.4 (× 2), 127.2,
127.1, 126.2, 124.9, 115.5; IR (film): 3435, 3055, 2921,
2853, 1650, 1604, 1492, 1452, 1211, 1034, 831, 767, 700
cm-1; HRMS (ESI) m/z calculated for C20H12BrOS- [M-H]-:
378.9798; found 378.9810.
2,4-Diphenylanthracen-1-ol (3w): 124.6 mg, 72% yield;
White solid; mp = 177–178 ºC; Eluant: EtOAc–petroleum
ether (1:20, Rf = 0.30). H NMR (400 MHz, DMSO-d6) 
1
9.44 (s, 1H), 8.35 (d, J = 9.1 Hz, 1H), 7.93 (d, J = 7.7 Hz,
1H), 7.87 (d, J = 9.2 Hz, 1H), 7.69 (d, J = 7.3 Hz, 2H),
7.63 (d, J = 8.6 Hz, 1H), 7.50–7.44 (m, 6H), 7.40–7.35 (m,
3H), 7.31 (s, 1H), 7.09 (t, J = 7.4 Hz, 1H); 13C NMR (100
MHz, DMSO-d6)  149.1, 144.8, 138.2, 133.1, 132.5,
132.2, 129.6 (× 2), 129.5, 129.1 (× 2), 129.0 (× 2), 128.5
(× 2), 128.4, 128.1, 127.6, 127.1, 127.0, 126.6, 126.3,
125.1, 125.0, 124.8, 121.3; IR (film): 3539, 3442, 2924,
2852, 1647, 1595, 1421, 1309, 1220, 1144, 818, 746, 700
cm-1; HRMS (ESI) m/z calculated for C26H17O- [M-H]-:
345.1285; found 345.1289.
4,6-Diphenylbenzofuran-7-ol (3bb): 65.8 mg, 46% yield;
White solid; mp = 72–73 ºC; Eluant: EtOAc–petroleum
1
ether (1:20, Rf = 0.30). H NMR (400 MHz, DMSO-d6) 
9.88 (s, 1H), 7.95 (d, J = 2.2 Hz, 1H), 7.88–7.81 (m, 2H),
7.69–7.59 (m, 2H), 7.49–7.41 (m, 4H), 7.39 (s, 1H), 7.36–
7.31 (m, 2H), 7.29 (d, J = 2.2 Hz, 1H); 13C NMR (100
MHz, DMSO-d6)  152.1, 147.1, 144.5, 138.6, 136.0,
129.6 (× 2), 128.6 (× 2), 127.9 (× 2), 127.8 (× 2), 126.9,
126.3, 126.2, 122.3, 117.9, 116.7, 105.0; IR (film): 3058,
2944, 2852, 1661, 1606, 1476, 1442, 1321, 1225, 1047,
6'-Methoxy-4'-phenyl-[1,2'-binaphthalen]-1'-ol
(3x):
135.0 mg, 72% yield; White solid; mp = 83–84 ºC; Eluant:
1
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
MHz, CDCl3)  8.31 (d, J = 9.2 Hz, 1H), 7.94 (d, J = 6.4
Hz, 2H), 7.78 (d, J = 8.3 Hz, 1H), 7.62–7.50 (m, 5H),
7.47–7.44 (m, 3H), 7.40–7.30 (m, 3H), 7.27–7.19 (m, 1H),
5.37 (s, 1H), 3.81 (s, 3H); 13C NMR (100 MHz, CDCl3) 
158.5, 148.3, 140.8, 134.2, 134.1, 133.8, 132.1, 131.4,
130.4, 130.2 (× 2), 128.9, 128.7, 128.6, 128.4 (× 2), 126.9,
126.9, 126.4, 125.9, 125.9, 124.6, 119.6, 117.6, 117.3,
-
760 cm-1; HRMS (ESI) m/z calculated for C20H13O2 [M-
H]-: 285.0921; found 285.0919.
8
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000625
Advanced Synthesis & Catalysis
1-Methyl-4,6-diphenyl-1H-indol-7-ol (3cc): 109.2 mg,
73% yield; Yellow solid; mp = 85–86 ºC; Eluant: EtOAc–
petroleum ether (1:20, Rf = 0.30). H NMR (400 MHz,
CDCl3)  7.58–7.52 (m, 2H), 7.51–7.44 (m, 4H), 7.38 (tt, J
= 14.7, 4.7 Hz, 4H), 6.99–6.89 (m, 2H), 6.68 (d, J = 3.1 Hz, 3390, 2920, 2852, 1655, 1597, 1487, 1441, 1346, 1232,
J = 11.0 Hz, 3H), 2.38 (s, 3H); 13C NMR (100 MHz,
DMSO-d6)  148.5, 137.9, 137.0, 136.2, 131.8, 131.8 (× 2),
131.5, 131.1 (× 2), 129.8 (× 2), 129.0 (× 2), 128.7, 126.5,
126.2, 125.3, 125.3, 122.9, 121.6, 120.1, 20.8; IR (film):
1
1H), 5.56 (s, 1H), 3.33 (s, 3H); 13C NMR (100 MHz,
CDCl3)  144.8, 140.1, 137.9, 135.2, 130.4 (× 2), 130.3,
129.6 (× 2), 129.3 (× 2), 127.7 (× 2), 127.2, 127.0, 126.5,
120.3, 119.1, 116.8, 98.5, 36.8; IR (film): 3415, 2923,
2855, 1718, 1477, 1352, 1257, 1208, 1072, 762, 702 cm-1;
HRMS (ESI) m/z calculated for C21H16NO [M-H]-:
298.1237; found 298.1236.
1105, 820, 760 cm-1; HRMS (ESI) m/z calculated for
C23H16BrO- [M-H]-: 387.0390; found 387.0384.
6-Methoxy-2-phenyl-4-(p-tolyl)naphthalen-1-ol
(4c):
139.5 mg, 82% yield; White solid; mp = 62–63 ºC; Eluant:
1
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
MHz, DMSO-d6)  9.35 (s, 1H), 8.38–8.34 (m, 1H), 7.66
(d, J = 8.0 Hz, 2H), 7.45–7.40 (m, 4H), 7.33–7.22 (m, 6H),
3.72 (s, 3H), 2.36 (s, 3H); 13C NMR (100 MHz, DMSO-d6)
 157.6, 148.7, 138.9, 137.5, 136.1, 132.8, 130.7, 130.2,
129.7 (× 2), 129.6 (× 2), 129.2 (× 2), 128.3 (× 2), 126.5,
124.9, 121.6, 121.1, 116.9, 104.2, 54.9, 20.8; IR (film):
3357, 2920, 2850, 1734, 1655, 1460, 1377, 1026, 771 cm-1;
2-(1H-indol-3-yl)-4-phenylnaphthalen-1-ol (3dd): 125.2
mg, 75% yield; White solid; mp = 75–76 ºC; Eluant:
1
EtOAc–petroleum ether (1:10, Rf = 0.30). H NMR (400
MHz, CDCl3)  8.47 (d, J = 7.9 Hz, 1H), 8.39 (s, 1H), 8.00
(d, J = 7.8 Hz, 1H), 7.73 (d, J = 7.8 Hz, 1H), 7.66–7.41 (m,
10H), 7.36 (t, J = 7.6 Hz, 1H), 7.26 (t, J = 7.5 Hz, 1H),
6.06 (s, 1H); 13C NMR (100 MHz, CDCl3)  148.3, 140.9,
136.6, 132.6, 131.9, 130.4 (× 2), 129.5, 128.3 (× 2), 126.9,
126.4, 126.3, 125.9, 125.4, 124.5, 123.4, 123.2, 122.7,
120.9, 119.9, 113.8, 112.3, 111.7; IR (film): 3416, 3056,
1723, 1674, 1599, 1572, 1505, 1456, 1414, 1245, 1218,
1095, 1031, 767, 743, 702 cm-1; HRMS (ESI) m/z
calculated for C24H16NO- [M-H]-: 334.1237; found
334.1227.
-
HRMS (ESI) m/z calculated for C24H19O2 [M-H]-:
339.1391; found 339.1372.
6-Chloro-2-(4-chlorophenyl)-4-(p-tolyl)naphthalen-1-ol
(4d): 141.8 mg, 75% yield; White solid; mp = 127–128 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  9.70 (s, 1H), 8.40 (d, J = 9.1 Hz,
1H), 7.72 (d, J = 1.9 Hz, 1H), 7.68 (d, J = 8.4 Hz, 2H),
7.57 (dd, J = 9.0, 1.7 Hz, 1H), 7.50 (d, J = 8.4 Hz, 2H),
7.42–7.28 (m, 5H), 2.38 (s, 3H); 13C NMR (100 MHz,
DMSO-d6)  148.8, 137.1, 136.6, 136.3, 132.4, 131.8,
131.5, 131.4 (× 2), 131.1, 130.3, 129.8 (× 2), 129.2 (× 2),
128.3 (× 2), 125.7, 125.6, 124.7, 123.9, 122.3, 20.8; IR
(film): 3519, 2920, 2852, 1620, 1568, 1487, 1298, 1203,
1084, 1038, 876, 823, 727, 685 cm-1; HRMS (ESI) m/z
calculated for C23H15Cl2O- [M-H]-: 377.0505; found
377.0497.
6-Methoxy-4-phenyl-2-(thiophen-2-yl)naphthalen-1-ol
(3ee): 129.1 mg, 78% yield; White solid; mp = 48–49 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, CDCl3)  8.33–8.23 (m, 1H), 7.55–7.44 (m,
4H), 7.43–7.38 (m, 3H), 7.28 (d, J = 3.5 Hz, 1H), 7.22–
7.15 (m, 3H), 6.17 (s, 1H), 3.77 (s, 3H); 13C NMR (100
MHz, CDCl3)  158.7, 148.2, 140.6, 139.3, 133.9, 131.8,
130.1 (× 2), 129.2, 128.5 (× 2), 128.1, 127.1, 126.6, 126.0,
124.7, 119.8, 117.8, 112.1, 104.9, 55.3; IR (film): 3507,
2928, 1624, 1607, 1578, 1494, 1470, 1426, 1384, 1354,
1268, 1232, 1180, 1037, 1008, 896, 776 cm-1; HRMS (ESI)
m/z calculated for C21H15O2S- [M-H]-: 331.0798; found
331.0785.
4-(4-Methoxyphenyl)-2-phenylnaphthalen-1-ol
(4e):
125.6 mg, 77% yield; White solid; mp = 117–118 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  9.33 (s, 1H), 8.38 (d, J = 8.2 Hz,
1H), 7.81 (d, J = 8.2 Hz, 1H), 7.67 (d, J = 7.2 Hz, 2H),
7.58–7.39 (m, 6H), 7.35 (t, J = 7.4 Hz, 1H), 7.28 (s, 1H),
7.06 (d, J = 8.6 Hz, 2H), 3.82 (s, 3H); 13C NMR (100 MHz,
DMSO-d6)  158.4, 148.3, 138.7, 132.3, 131.5, 131.5,
131.0 (× 2), 129.7 (× 2), 129.3, 128.3 (× 2), 126.7, 126.3,
126.3, 125.3, 125.2, 122.9, 122.9, 113.9 (× 2), 55.2; IR
(film): 3386, 2924, 2846, 1572, 1508, 1441, 1302, 1236,
1176, 1020, 831, 764, 706 cm-1; HRMS (ESI) m/z
2-Phenyl-4-(p-tolyl)naphthalen-1-ol (4a): 122.5 mg, 79%
yield; White solid; mp = 83–84 ºC; Eluant: EtOAc–
1
petroleum ether (1:20, Rf = 0.30). H NMR (400 MHz,
DMSO-d6)  9.38 (s, 1H), 8.40 (d, J = 8.4 Hz, 1H), 7.81 (d,
J = 8.3 Hz, 1H), 7.67 (d, J = 7.1 Hz, 2H), 7.54 (d, J = 7.1
Hz, 1H), 7.50–7.43 (m, 3H), 7.36 (t, J = 8.4 Hz, 3H), 7.33–
7.25 (m, 3H), 2.38 (s, 3H); 13C NMR (100 MHz, DMSO-
d6)  148.4, 138.8, 137.2, 136.2, 131.7, 131.4, 129.9 (× 2),
129.7 (× 2), 129.3, 129.1 (× 2), 128.3 (× 2), 126.8, 126.4,
126.3, 125.3, 125.2, 122.9, 122.9, 20.8; IR (film): 3442,
3028, 2924, 2854, 1657, 1599, 1508, 1450, 1209, 1047,
820, 764, 696 cm-1; HRMS (ESI) m/z calculated for
C23H17O- [M-H]-: 309.1285; found 309.1279.
-
calculated for C23H17O2 [M-H]-: 325.1234; found
325.1231.
6-Chloro-4-(4-methoxyphenyl)-2-phenylnaphthalen-1-
ol (4f): 140.4 mg, 78% yield; White solid; mp = 128–129
1
ºC; Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). H
NMR (400 MHz, DMSO-d6)  9.59 (s, 1H), 8.40 (d, J =
9.0 Hz, 1H), 7.72 (s, 1H), 7.66 (d, J = 7.4 Hz, 2H), 7.56 (d,
J = 8.9 Hz, 1H), 7.51–7.39 (m, 4H), 7.36 (d, J = 12.0 Hz,
2H), 7.08 (d, J = 8.2 Hz, 2H), 3.82 (s, 3H); 13C NMR (100
MHz, DMSO-d6)  158.6, 148.5, 138.3, 132.3, 131.5,
131.2, 131.0 (× 2), 130.7 (× 2), 129.6 (× 2), 128.4 (× 2),
126.9, 125.6, 125.6, 124.8, 123.9, 123.6, 114.1 (× 2), 55.2;
IR (film): 3491, 2922, 2850, 1612, 1568, 1510, 1308, 1248,
2-(4-Bromophenyl)-4-(p-tolyl)naphthalen-1-ol
(4b):
151.3 mg, 78% yield; White solid; mp = 84–85 ºC; Eluant:
1
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
MHz, DMSO-d6)  9.47 (s, 1H), 8.39 (d, J = 8.4 Hz, 1H),
7.80 (d, J = 8.3 Hz, 1H), 7.63 (s, 4H), 7.57–7.52 (m, 1H),
7.49 (d, J = 7.9 Hz, 1H), 7.37 (d, J = 7.9 Hz, 2H), 7.29 (d,
9
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000625
Advanced Synthesis & Catalysis
1207, 1031, 768, 698 cm-1; HRMS (ESI) m/z calculated for
837, 764 cm-1; HRMS (ESI) m/z calculated for C22H14FO
-
C23H16ClO2 [M-H]-: 359.0844; found 359.0836.
[M-H]-: 313.1034; found 313.1037.
4-(2-Chlorophenyl)-2-phenylnaphthalen-1-ol (4k): 121.7
mg, 74% yield; White solid; mp = 59–60 ºC; Eluant:
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
MHz, CDCl3)  8.47 (d, J = 8.3 Hz, 1H), 7.66 (d, J = 7.6
Hz, 2H), 7.63–7.55 (m, 5H), 7.53 (d, J = 6.7 Hz, 1H), 7.48
(t, J = 6.2 Hz, 2H), 7.44–7.41 ((m, 2H), 7.39 (s, 1H), 6.03
(s, 1H); 13C NMR (100 MHz, CDCl3)  147.8, 139.1, 137.1,
134.5, 132.6, 132.3, 129.9, 129.7 (× 2), 129.6, 129.4 (× 2),
128.9, 128.9, 128.0, 126.8, 126.6, 125.8, 125.6, 124.3,
4-(4-Methoxyphenyl)-6-methyl-2-phenylnaphthalen-1-
ol (4g): 127.5 mg, 75% yield; White solid; mp = 67–68 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  9.29 (s, 1H), 8.30 (d, J = 8.6 Hz,
1H), 7.66 (d, J = 7.4 Hz, 2H), 7.58 (s, 1H), 7.44 (t, J = 7.5
Hz, 2H), 7.39 (t, J = 6.8 Hz, 3H), 7.32 (t, J = 7.3 Hz, 1H),
7.24 (s, 1H), 7.05 (d, J = 8.4 Hz, 2H), 3.81 (s, 3H), 2.39 (s,
3H); 13C NMR (100 MHz, DMSO-d6)  158.4, 148.3,
138.9, 135.5, 132.5, 131.8, 131.0 (× 2), 130.9, 129.7 (× 2),
1
129.5, 128.3 (× 2), 127.3, 126.6, 124.6, 124.3, 123.0, 122.1, 122.8, 120.7; IR (film): 3529, 3058, 2923, 1622, 1576,
113.9 (× 2), 55.1, 21.6; IR (film): 3543, 3028, 2925, 2841,
1732, 1606, 1510, 1456, 1306, 1246, 1182, 1041, 831, 775,
704 cm-1; HRMS (ESI) m/z calculated for C24H19O2 [M-H]-
: 339.1391; found 339.1399.
1499, 1437, 1374, 1308, 1209, 1048, 856, 759, 703 cm-1;
HRMS (ESI) m/z calculated for C22H14ClO- [M-H]-:
329.0739; found 329.0743.
4-(3-Fluorophenyl)-2-phenylnaphthalen-1-ol (4l): 100.5
mg, 64% yield; White solid; mp = 81–82 ºC; Eluant:
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
MHz, CDCl3)  8.43 (d, J = 8.2 Hz, 1H), 7.93 (d, J = 8.3
Hz, 1H), 7.67–7.43 (m, 8H), 7.37 (s, 1H), 7.33 (d, J = 7.6
Hz, 1H), 7.27 (d, J = 11.2 Hz, 1H), 7.14 (t, J = 8.3 Hz, 1H),
5.96 (s, 1H); 13C NMR (100 MHz, CDCl3)  162.8 (d, JCF
= 245.0 Hz), 147.8, 142.9 (d, JCF = 7.0 Hz), 137.1, 131.9,
2-(4-Fluorophenyl)-6-methoxy-4-(4-methoxyphenyl)
naphthalen-1-ol (4h): 151.5 mg, 81% yield; White solid;
mp = 135–136 ºC; Eluant: EtOAc–petroleum ether (1:20,
Rf = 0.30). 1H NMR (400 MHz, DMSO-d6)  9.32 (s, 1H),
8.31 (d, J = 9.2 Hz, 1H), 7.67 (dd, J = 8.7, 5.7 Hz, 2H),
7.44 (d, J = 8.6 Hz, 2H), 7.31–7.20 (m, 5H), 7.05 (d, J =
8.6 Hz, 2H), 3.82 (s, 3H), 3.73 (s, 3H); 13C NMR (100
1
MHz, DMSO-d6)  161.1 (d, JCF = 241.0 Hz), 158.3, 157.6, 131.6 (d, JCF = 2.0 Hz), 129.8, 129.8, 129.4, 128.7, 128.2,
148.5, 135.1 (d, JCF = 3.0 Hz), 132.9, 132.5, 131.5 (d, JCF
=
126.9, 126.1 (d, JCF = 3.0 Hz), 125.7, 125.5, 124.6, 122.9,
120.9, 117.3 (d, JCF = 21.0 Hz), 113.9 (d, JCF = 21.0 Hz);
IR (film): 3535, 3062, 2924, 2856, 1578, 1496, 1443, 1371,
1308, 1189, 1050, 869, 773, 704 cm-1; HRMS (ESI) m/z
calculated for C22H14FO- [M-H]-: 313.1034; found
313.1030.
8.0 Hz, × 2), 130.9 (× 2), 130.4, 129.9, 124.9, 121.5, 120.1,
116.9, 115.0 (d, JCF = 21.0 Hz, × 2), 113.9 (× 2), 104.32,
55.1, 54.9; IR (film): 3398, 2954, 2835, 1514, 1508, 1431,
1309, 1238, 1101, 1022, 903, 827 cm-1; HRMS (ESI) m/z
-
calculated for C24H18FO3 [M-H]-: 373.1245; found
373.1240; CCDC 1940564 contains the crystallographic
data for 4h that can be obtained free of charge from the
CCDC via www.ccdc.cam.ac.uk/data_request/cif.
2-Phenyl-4-(pyridin-2-yl)naphthalen-1-ol (4m): 93.6 mg,
63% yield; White solid; mp = 190–191 ºC; Eluant: EtOAc–
petroleum ether (1:20, Rf = 0.30). H NMR (400 MHz,
1
4-(4-Nitrophenyl)-2-phenylnaphthalen-1-ol (4i): 133.0
mg, 78% yield; Yellow solid; mp = 64–65 ºC; Eluant:
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
DMSO-d6)  9.55 (s, 1H), 8.73 (d, J = 4.4 Hz, 1H), 8.42 (d,
J = 8.3 Hz, 1H), 8.16 (d, J = 8.3 Hz, 1H), 7.90 (t, J = 7.7
Hz, 1H), 7.70–7.67 (m, 3H), 7.59–7.45 (m, 5H), 7.41–7.34
(m, 2H); 13C NMR (100 MHz, DMSO-d6)  158.5, 149.5,
149.1, 138.6, 136.8, 131.1, 130.4, 129.6 (× 2), 128.3 (× 2),
126.8, 126.5, 126.2, 125.5, 125.2, 124.8, 122.8, 122.7,
121.9; IR (film): 2925, 1264, 733, 703 cm-1; HRMS (ESI)
m/z calculated for C21H14NO- [M-H]-: 296.1081; found
296.1078.
1
MHz, CDCl3)  8.41 (d, J = 8.2 Hz, 1H), 8.31 (d, J = 8.1
Hz, 2H), 7.80 (d, J = 8.2 Hz, 1H), 7.66 (d, J = 8.1 Hz, 2H),
7.60–7.43 (m, 7H), 7.33 (s, 1H), 6.02 (s, 1H); 13C NMR
(100 MHz, C DCl3)  148.5, 147.6, 146.9, 136.7, 131.6,
131.1 (× 2), 130.3, 129.8 (× 2), 129.4 (× 2), 129.0, 128.4,
127.4, 125.9, 124.9, 124.7, 123.7 (× 2), 123.2, 121.0; IR
(film): 3512, 3062, 2924, 2851, 1723, 1586, 1510, 1342,
1211, 1045, 852, 760, 698 cm-1; HRMS (ESI) m/z
calculated for C22H14NO3 [M-H]-: 340.0979; found
340.0982.
Methyl 4-hydroxy-3-phenyl-1-naphthoate (6a): 101.5
mg, 73% yield; White solid; mp = 88–89 ºC; Eluant:
1
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
MHz, DMSO-d6)  10.24 (s, 1H), 8.96 (d, J = 8.4 Hz, 1H),
8.43 (d, J = 8.0 Hz, 1H), 8.16 (s, 1H), 7.74–7.64 (m, 1H),
7.63–7.59 (m, 3H), 7.49 (t, J = 7.6 Hz, 2H), 7.39 (t, J = 7.4
Hz, 1H), 3.88 (s, 3H); 13C NMR (100 MHz, DMSO-d6) 
166.8, 153.9, 137.8, 134.2, 131.9, 129.6 (× 2), 128.5 (× 2),
128.1, 127.2, 125.9, 125.6, 125.3, 123.1, 121.9, 117.5,
51.9; IR (film): 3398, 2947, 1685, 1566, 1052, 1439, 1250,
1053, 922, 787, 692 cm-1; HRMS (ESI) m/z calculated for
4-(4-Fluorophenyl)-2-phenylnaphthalen-1-ol (4j): 124.0
mg, 79% yield; White solid; mp = 59–60 ºC; Eluant:
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
MHz, CDCl3)  8.38 (d, J = 8.3 Hz, 1H), 7.83 (d, J = 8.3
Hz, 1H), 7.60–7.39 (m, 9H), 7.29 (s, 1H), 7.15 (t, J = 8.6
Hz, 2H), 5.90 (s, 1H); 13C NMR (100 MHz, CDCl3) 
162.2 (d, JCF = 244.0 Hz), 147.5, 137.2, 136.6 (d, JCF = 3.0
Hz), 132.3, 131.9, 131.8 (d, JCF = 8.0 Hz, × 2), 131.8,
129.7 (× 2), 129.4 (× 2), 128.7, 128.1, 126.8, 125.6, 124.6,
1
-
C18H13O3 [M-H]-: 277.0870; found 277.0866. CCDC
1940565 contains the crystallographic data for 6a that can
122.9, 120.9, 115.2 (d, JCF = 21.0 Hz, × 2); IR (film): 3428, be obtained free of charge from the CCDC via
3049, 2921, 2853, 2320, 1505, 1452, 1305, 1214, 1045, www.ccdc.cam.ac.uk/data_request/cif.
10
This article is protected by copyright. All rights reserved.

10.1002/adsc.202000625
Advanced Synthesis & Catalysis
8.4 Hz, 1H), 7.93 (dd, J = 7.8, 1.3 Hz, 1H), 7.83 (d, J = 9.0
Hz, 1H), 7.74 (s, 1H), 7.65–7.54 (m, 6H), 7.48 (ddd, J =
5.5, 4.3, 2.6 Hz, 1H), 6.11 (s, 1H), 3.96 (s, 3H); 13C NMR
(100 MHz, CDCl3)  172.5, 150.5, 135.9, 133.4, 130.1,
129.9 (× 2), 129.3 (× 2), 129.0, 128.7, 128.6 (× 2), 127.7,
127.2, 126.7, 125.8, 122.9, 122.8, 122.4, 120.5, 52.7; IR
(film): 2924, 2854, 1712, 1574, 1429, 1225, 1109, 1007,
825, 769, 702 cm-1; HRMS (ESI) m/z calculated for
C22H15O3 [M-H]-: 327.1027; found 327.1036.
Methyl
3-(4-bromophenyl)-4-hydroxy-1-naphthoate
(6b): 135.3 mg, 76% yield; White solid; mp = 153–154 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, CDCl3)  9.04 (d, J = 8.7 Hz, 1H), 8.35 (d, J =
8.2 Hz, 1H), 8.16 (s, 1H), 7.68–7.65 (m, 3H), 7.57 (t, J =
7.2 Hz, 1H), 7.40 (d, J = 8.3 Hz, 2H), 6.23 (s, 1H), 3.95 (s,
3H); 13C NMR (100 MHz, CDCl3)  167.6, 152.1, 135.1,
133.1, 132.9 (× 2), 132.7, 131.1 (× 2), 128.7, 126.1, 125.9,
124.5, 122.8, 122.7, 119.2, 119.2, 52.0; IR (film): 3369,
2924, 2852, 1684, 1566, 1498, 1433, 1375, 1219, 1126,
1049, 781, 735 cm-1; HRMS (ESI) m/z calculated for
[20]
Methyl 4-hydroxy-1,3-diphenyl-2-naphthoate (6g):
C18H12BrO3 [M-H]-: 354.9975; found 354.9971. CCDC
1940559 contains the crystallographic data for 6b that can
be obtained free of charge from the CCDC via
www.ccdc.cam.ac.uk/data_request/cif.
-
76.7 mg, 43% yield; White solid; mp = 58–59 ºC; Eluant:
1
EtOAc–petroleum ether (1:20, Rf = 0.30). H NMR (400
MHz, CDCl3)  8.36 (d, J = 8.3 Hz, 1H), 7.68–7.37 (m,
13H), 5.70 (s, 1H), 3.21 (s, 3H); 13C NMR (100 MHz,
CDCl3)  169.1, 147.9, 137.9, 134.3, 132.7, 132.3, 130.7
(2C), 130.4 (× 2), 130.1, 129.5 (× 2), 128.8, 128.1 (× 2),
127.6, 127.2, 126.8, 126.4, 124.4, 122.6, 118.3, 51.6; IR
(film): 3531, 2922, 1732, 1504, 1382, 1310, 1284, 1230,
1065, 896, 702 cm-1; HRMS (ESI) m/z calculated for
Methyl 7-fluoro-4-hydroxy-3-phenyl-1-naphthoate (6c):
109.6 mg, 74% yield; White solid; mp = 127–128 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, CDCl3)  8.80 (dd, J = 12.3, 2.5 Hz, 1H), 8.36
(dd, J = 9.3, 6.1 Hz, 1H), 8.27 (s, 1H), 7.58–7.41 (m, 5H),
7.31 (ddd, J = 9.3, 7.8, 2.6 Hz, 1H), 6.34 (s, 1H), 3.94 (s,
-
C24H17O3 [M-H]-: 353.1183; found 353.1190.
3H); 13C NMR (100 MHz, CDCl3)  167.3, 162.7 (d, JCF
=
Dimethyl
4-hydroxy-3-phenylnaphthalene
-1,2-
dicarboxylate (6h): 122.7 mg, 73% yield; White solid; mp
= 65–66 ºC; Eluant: EtOAc–petroleum ether (1:15, Rf =
0.30). H NMR (400 MHz, CDCl3)  8.38–8.28 (m, 2H),
245.0 Hz), 152.5, 135.8, 134.9, 134.2 (d, JCF = 10.0 Hz),
129.9 (× 2), 129.4 (× 2), 128.6, 125.7 (d, JCF = 9.0 Hz),
121.5, 119.9, 118.1 (d, JCF = 6.0 Hz), 116.0 (d, JCF = 25.0
Hz), 110.1 (d, JCF = 24.0 Hz), 52.0; IR (film): 3398, 2922,
2850, 1697, 1630, 1570, 1500, 1223, 1115, 879, 771, 702
1
7.70–7.56 (m, 2H), 7.56–7.43 (m, 3H), 7.43–7.34 (m, 2H),
5.93 (s, 1H), 3.95 (s, 3H), 3.53 (s, 3H); 13C NMR (100
MHz, CDCl3)  168.4, 167.8, 151.2, 133.6, 133.5, 130.8,
130.3 (× 2), 129.5 (× 2), 129.0, 128.6, 127.1, 125.9, 124.3,
122.8, 120.9, 118.8, 52.6, 52.2; IR (film): 3514, 2950,
1723, 1567, 1498, 1376, 1294, 1226, 1071, 994, 743 cm-1;
-
cm-1; HRMS (ESI) m/z calculated for C18H12FO3 [M-H]-:
295.0776; found 295.0777.
Methyl
7-chloro-4-hydroxy-3-phenyl-1-naphthoate
-
HRMS (ESI) m/z calculated for C20H15O5 [M-H]-:
(6d): 123.2 mg, 79% yield; White solid; mp = 142–143 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  10.49 (s, 1H), 9.03 (s, 1H), 8.52–
8.35 (m, 1H), 8.19 (s, 1H), 7.69–7.56 (m, 3H), 7.55–7.46
(m, 2H), 7.44–7.34 (m, 1H), 3.87 (s, 3H); 13C NMR (100
MHz, DMSO-d6)  166.4, 154.2, 137.4, 135.7, 133.4,
132.6, 129.5 (× 2), 128.6 (× 2), 127.4, 126.0, 125.6, 124.4,
124.1, 122.6, 116.2, 51.9; IR (film): 3502, 2924, 1703,
1566, 1491, 1377, 1213, 1088, 1045, 877, 773, 704 cm-1;
335.0925; found 335.0931.
Acknowledgements
We are grateful for financial support from National Natural
Science Foundation of China (Nos. NSFC-21572178, NSFC-
21702162 and NSFC-21971206), Education Department of
Shaanxi Provincial Government (No. 17JK0732).
-
HRMS (ESI) m/z calculated for C18H12ClO3 [M-H]-:
311.0480; found 311.0475.
References
Methyl 4-hydroxy-7-methoxy-3-phenyl-1-naphthoate
(6e): 113.9 mg, 74% yield; White solid; mp = 133–134 ºC;
Eluant: EtOAc–petroleum ether (1:20, Rf = 0.30). 1H NMR
(400 MHz, DMSO-d6)  10.21 (s, 1H), 8.50 (d, J = 2.5 Hz,
1H), 8.34 (d, J = 9.3 Hz, 1H), 8.17 (s, 1H), 7.58 (d, J = 7.2
Hz, 2H), 7.48 (t, J = 7.6 Hz, 2H), 7.37 (t, J = 7.3 Hz, 1H),
7.26 (dd, J = 9.3, 2.5 Hz, 1H), 3.91 (s, 3H), 3.87 (s, 3H);
13C NMR (100 MHz, DMSO-d6)  166.9, 159.1, 154.4,
137.9, 135.1, 134.0, 129.5 (× 2), 128.5 (× 2), 127.0, 124.9,
120.9, 120.4, 117.4, 115.7, 104.4, 55.1, 51.7; IR (film):
3404, 2922, 2850, 1689, 1572, 1495, 1425, 1190, 1101,
1026, 860, 702, 594 cm-1; HRMS (ESI) m/z calculated for
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10.1002/adsc.202000625
Advanced Synthesis & Catalysis
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Iron-Promoted Domino Dehydrogenative
Annulation of Deoxybenzoins and Alkynes
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