C(sp2)-C(sp2) Suzuki cross-coupling of arylammonium salts catalyzed by a stable Pd–NHC complex

Article abstract of DOI:10.1016/j.tet.2021.132431

We have developed the Suzuki-Miyaura cross-coupling of aryl ammonium salts via C–N bond activation catalyzed by an easily prepared and bench-stable palladium-N-heterocyclic carbene complex. The reaction proceeded well under mild conditions with phenylboronic acid, pinacol ester or anhydride and provided yields of products up to 97% with good functional group compatibility. The direct arylation of arylamine can be performed by a two-step one-pot process and the protocol can be performed on the gram scale.

Full text of DOI:10.1016/j.tet.2021.132431

Tetrahedron xxx (xxxx) xxx
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
C(sp2)-C(sp2) Suzuki cross-coupling of arylammonium salts catalyzed
by a stable PdeNHC complex
Huiling Tang 1, Mengna Liu 1, Meiqi Zhu, Benqiang Cui, Yanhui Shi*, Changsheng Cao**
School of Chemistry and Material Science, Jiangsu Normal University, Xuzhou, 221116, China
a r t i c l e i n f o
a b s t r a c t
Article history:
We have developed the Suzuki-Miyaura cross-coupling of aryl ammonium salts via CeN bond activation
catalyzed by an easily prepared and bench-stable palladium-N-heterocyclic carbene complex. The re-
action proceeded well under mild conditions with phenylboronic acid, pinacol ester or anhydride and
provided yields of products up to 97% with good functional group compatibility. The direct arylation of
arylamine can be performed by a two-step one-pot process and the protocol can be performed on the
gram scale.
Received 23 June 2021
Received in revised form
26 August 2021
Accepted 30 August 2021
Available online xxx
© 2021 Published by Elsevier Ltd.
Keywords:
Pd-NHC complex
Suzuki reaction
Ammonium salt
CeN bond activation
1. Introduction
amines [11]. Until now, the coupling reaction of trimethylammo-
nium salts has been successfully applied in Kumada [12], Negishi
Transition-metal-catalyzed cross-coupling reactions, such as
SuzukieMiyaura [1], Heck [2], Stille [3], Kumada [4], Negishi [5],
Hiyama [6], and Sonogashira [7] reactions are highly practical ap-
proaches for the formation of CeC bonds. Among these cross-
coupling reactions, the SuzukieMiyaura reaction has been proven
to be the most attractive method to form the CeC bond, because
organoboron reagents involved in the reaction have air- and
moisture-stability, good functional group tolerance, low toxicity
and wide availability [8].
Electrophiles employed in the Suzuki reaction are principally
aryl halides and oxygen-containing compounds, such as triflates,
mesylates/tosylates and phosphates [9]. Recently, the nitrogen-
containing electrophilic partners have been developed due to the
abundance of CeN bonds in organic intermediates, therapeutic
drugs, and organic materials [10]. Among them, the research of
using quaternary ammonium salts as coupling partners has
attracted considerable attention.10g Quaternary ammonium salts
are not only air and thermally stable, but only readily available
through quaternization of a large variety of tertiary aryl/alkyl
[13], Still [14], Suzuki [15], BuchwaldeHartwig [16], Sonogashira
[17] and other cross-couplings [18]. Although several approaches
on the C(Sp2)-C(Sp3) cross-coupling of benzyl trimethylammonium
salts with boronic acids have been developed [15b-15f], only one
method on the C(Sp2)-C(Sp2) cross-coupling of aryl trimethy-
lammonium salts was reported by Macmillan until now (Scheme 1)
[15a]. In Macmillan's reaction, the extremely air-sensitive and
thermally unstable Ni(COD)2 was employed as the catalyst, so it
would be interested to develop an alternative approach for the
Suzuki coupling of arylammonium salts using an air-stable, robust,
and user-friendly catalyst.
Herein, we describe the Suzuki reaction of aryl-
trimethylammonium salts with phenylboronic acid, anhydride and
ester via CeN bond activation catalyzed by a well-defined and
stable PdeNHC complex in good to excellent yields.
2. Results and discussion
In our previous work, we found that the stable and well-defined
PdeNHC complex, SIPr-PdCl2-Py (Fig.1) was an effective catalyst for
the Sonogashira reaction of trimethylammonium salts, suggesting
that the Pd(0)-NHC readily inserts into the CeN bond of phenyl-
ammonium via oxidation addition.17 Triggered by this work, we
envisaged that the PdeNHC complex could be effective for the
Suzuki cross-coupling of aryl quaternary ammonium salt, as Pd
* Corresponding author.
** Corresponding author.
E-mail address: yhshi@jsnu.edu.cn (Y. Shi).
H. Tang and M. Liu contributed equally to this article.
1
https://doi.org/10.1016/j.tet.2021.132431
0040-4020/© 2021 Published by Elsevier Ltd.
Please cite this article as: H. Tang, M. Liu, M. Zhu et al., C(sp2)-C(sp2) Suzuki cross-coupling of arylammonium salts catalyzed by a stable PdeNHC
complex, Tetrahedron, https://doi.org/10.1016/j.tet.2021.132431

H. Tang, M. Liu, M. Zhu et al.
Tetrahedron xxx (xxxx) xxx
range of boronic acids were chosen to react with arylammonium
salt 1 (Table 2, 3e29). Various substituted phenyl boronic acid
bearing either electron-donating or electron-withdrawing group
could be successfully converted to the corresponding phenyl-
naphthalene in good to excellent yields. There was no obvious
steric effect when the phenylboronic acid had a group in the ortho
position (Table 2, 20e22). Various useful functional groups, such as
thioether, trimethylsilyl, trifluoro, ether, fluoro, cyano, nitro, ester,
keto, amide and vinyl groups were well tolerated to provide desired
coupling products in good to high yields (Table 2, 6e7, 9e17 and
24). However, Cl substitution on the phenylboronic acid interfered
with the reaction and resulted in a low yield of 12 (36%). It is
assumed that the chloride reacted competitively with ammonium
salt 1 in the reaction of phenylboronic acid, which was confirmed
by formation of a large amount of biphenyl in the one-pot reaction
of phenylchloride, phenylboronic acid and 1 under the same con-
ditions. The reaction of naphthylboronic acid with 1 proceeded well
and 1,10-binaphthalene (Table 2, 23) was obtained in 80% of yield.
Moreover, heterocyclic boronic acids, such as dibenzofuran,
dibenzothiophene, thiophene, benzodioxole and pyridine are
applicable to this system, and the corresponding reactions with 1
provided the desired products in moderate to good yields (Table 2,
25e29).
Furthermore, a few arylammonium triflates were examined in
the Suzuki reaction of methylphenylboronic acid (Table 3). The
trimethylammonium triflate with a fused aromatic ring could
partake in this reaction smoothly (Table 3, 30e32). For example, 2-
indolyltrimethylammonium triflate smoothly reacted with 4-
methylbenzeneboronic acid to give 95% of 30. Both methoxy-
substituted electron-rich and cyano-substituted electron-deficient
1-naphthyltrimethylammonium triflates showed good activity in
the reaction (Table 3, 31e32). The electron-deficient 2-
pyridyltrimethylammonium triflate smoothly reacted with 4-
methylbenzeneboronic acid to afford 33 in 90% yield. Unfortu-
nately, in the Suzuki reaction of phenyltrimethylammonium tri-
flate, only N,N-dimethylaniline decomposed from the ammonium
salt was observed without any cross-coupling product (Table 3, 34).
The better activity of naphthyl group over phenyl group in qua-
ternary ammonium salt was observed in the CeP cross coupling
reaction of ammonium salt [19]. When N,N-dimethyl-N-phenyl-1-
naphthyldimethylammonium triflate was employed in the reac-
tion, the coupling product 4 was exclusively generated in 75% yield,
suggesting that the reaction proceeded selectively at the side of
naphthyl group. The protocol is applicable to benzyl ammonium
salt as well, and 76% yield of 35 was isolated with benzyldime-
thylammonium triflate.
Scheme 1. C(sp2)-C(sp2) Suzuki cross-coupling of aryltrimethylammonium salts via
CeN bond activation.
catalysts have been successfully employed in a wide range of Suzuki
coupling reaction through transmetalation with aryl boronic acids.
Therefore, our investigation into the Suzuki reaction of ary-
lammonium salts started with N,N,N-trimethylnaphthalen-1-
aminium triflate (1), phenylboronic acid (2) and a series of stable
Pd catalyst. It was gratifying to note that the desired product, 1-
phenylnaphthalene (3) was obtained in 42% of yield when SIPr-
PdCl2-Py (5 mol%) was employed (Table 1, entry 1). However, when
less electron-rich IPr-PdCl2-Py was used, the yield of 3 decreased
nearly 30% (Table 1, entry 2). In the cases of commercially available
Pd(PPh3)2Cl2, PdCl2 or Pd(OAc)2 with the addition of the phosphine
ligand PCy3, PPh3, dppe, dppf, Xphos, t-BuXphos and Ruphos, only
less than 20% of 3 were observed (Table 1, entries 3e11). PdCl2 with
the N-heterocycle carbene (NHC) ligand SIPr or IPr provided less
than 30% of 3 (Table 1, entries 10e11). Because a large amount of
N,N-dimethylnaphthalen-1-amine decomposed from 1 was detec-
ted by GC-MS in the reaction mixture, the amount of 1 was raised to
2 equivalent, which led to 53% of 3 (Table 1, entry 14). The amount
of catalyst loading and base slightly influence the reaction, and 73%
of 3 was afforded when doubling the amount of SIPr-PdCl2-Py to
10 mol% and t-BuONa to 2 equivalent (Table 1, entries 15e16).
Subsequently, the screening of bases indicates that 3 could be
afforded in 79% yield when CsF was employed, while the yield of 3
was generally lower than 55% when other bases were used (Table 1,
entries 17e22). Finally, different solvents were also screened, and
the highest yield was observed with THF used as the solvent
(Table 1, entries 23e27). It was found that elevating the reaction
temperature would facilitate the reaction, and the highest reaction
yield was reached at 80 ꢀC in 86% (Table 1, entries 28e30).
Furthermore, the arylboronic acid can be replaced by arylbor-
onic acid ester in this protocol. In the reaction of arylboronic acid
pinacol ester with 1, the corresponding products were efficiently
obtained with moderate to good yields (Table 4). However,
With the optimized reaction conditions in hand, the scope and
generality of the ammonium Suzuki reaction was explored. A wide
Fig. 1. Structure of PdeNHC complexes and NHC Ligands.
2

H. Tang, M. Liu, M. Zhu et al.
Tetrahedron xxx (xxxx) xxx
Table 1
Optimization of the reaction conditionsa.
Entrya
Cat. (mol%)
Ligand
1 (equiv)
Base (eq.)
Temp (oC)
Yield (%)b
1
2
3
4
5
6
7
8
SIPr-PdCl2-Py (5)
IPr-PdCl2-Py (5)
Pd(PPh3)2Cl2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
PdCl2 (5)
1
1
1
1
2
2
2
2
2
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (1.5)
t-BuONa (2)
CsF (2)
Cs2CO3 (2)
K3PO4 (2)
t-BuOK (2)
t-BuOLi (2)
K3PO4$3H2O (2)
CsF (2)
CsF (2)
CsF (2)
CsF (2)
CsF (2)
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
70
80
90
42
14
trace
trace
13
17
14
15
13
trace
trace
29
10
53
65
73
79
35
24
55
10
42
73
53
6
PPh3
PPh3
dppe
dppf
Xphos
t-BuXphos
Ruphos
PPh3
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23c
24d
25e
26f
27g
28
29
30
PdCl2 (5)
PdCl2 (5)
PdCl2 (5)
PCy3
SIPr . HCl
IPr . HCl
SIPr-PdCl2-Py (5)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
SIPr-PdCl2-Py (10)
6
39
81
86
85
CsF (2)
CsF (2)
CsF (2)
a
Conditions: 1 (1e2 equiv.), 2 (0.2 mmol), catalyst (5e10 mol%), ligand (10 mol%), base (1.5e2 equiv.), THF (1 mL), 60e90 ꢀC under N2 atmosphere, unless noted otherwise.
b
c
d
e
f
HPLC yield with N-phenylbenzamide as the internal standard.
Dioxane as the solvent.
DMF as the solvent.
i-PrOH as the solvent.
CH3CN as the solvent.
g
Toluene as the solvent.
compared to the reaction with boronic acid, the slightly decreased
yield was observed in the reaction with pinacol ester (Table 4,
36e41 and 44e48). For example, the reaction of 1 with 2-(4-
naphthyltrimethylammonium triflate was prepared in-situ and
then used directly without isolation and purification (Scheme 3).
Moreover, 0.66 g of 3 in 81% yield was obtained when the reaction
scale was increased 8-fold to 4 mmol of 2 and 8 mmol of 1 (Scheme
4). These yields in two-step one-pot and scale-up reactions are
comparable with the yield of the small-scale one-step reaction
(Table 2, 3).
Based on our previous investigation [17], a possible mechanism
for this transformation is shown in Scheme 5. First, the oxidative
addition of SIPr-Pd(0)-Py A which is generated in situ, with tri-
methylbenzylicammonium salt I produced intermediate B and
released trimethylamine. Then intermediate B converted to a new
complex C by a transmetalation with boronic acid II. Finally, the
cross coupling product III was obtained upon reductive elimination
of C.
fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
achieved
81% yield of 40 (Table 4, 40). The yield is slightly low compared with
that of the reaction with (4-fluorophenyl)boronic acid (Table 2, 11,
91%). Both electron-withdrawing group and electron-donating
group on pinacol esters were none notable effective in the reac-
tion, moreover, many sensitive groups, even aldehyde could be
tolerated in the reaction (43). Although ortho-, meta-, and para-
methoxyphenylboronic acid pinacol esters reacted smoothly with
1 to give coupling products in good yields, yields of ortho and para
product are slightly reduced, showing steric effect in the reaction
(44e46). Heterocyclic boronic acid pinacol esters, such as thio-
phene and furan are applicable in the reaction (48e49). Finally,
phenylboronic anhydride can also be used in this protocol, afford-
ing 1-phenylnaphthalene (50) in 87% yield (Scheme 2).
3. Conclusion
To demonstrate the practicality of the protocol, amine was
directly used in a two-step one-pot process. Dimethylnaphthyl-
amine can be converted to 3 in an 80% overall yield via methylation
by methyl triflate followed by the Pd-catalyzed Suzuki reaction
In summary, we have developed a palladium-catalyzed Suzuki
coupling of ammonium triflates with arylboronic acids, anhydride
and pinacol ester through CeN bond cleavage. The readily available
palladium catalyst is air- and moisture-stable, and the reaction
with
phenylboronic
acid
(2).
In
the
reaction, 1-
3

H. Tang, M. Liu, M. Zhu et al.
Tetrahedron xxx (xxxx) xxx
Table 2
The Suzuki cross-coupling of arylboronic acids with 1.
proceeded well under mild conditions providing yields of products
up to 97%. This reaction has a broad scope of organoboron sub-
strates, and exhibits good functional group compatibility Moreover,
the direct arylation of arylamine can be performed by a two-step
one-pot process without isolation of the ammonium salt and the
protocol can be performed on the gram scale.
Compared to the reported Ni catalyst system [15a], the PdeNHC
catalyst is user-friendly and easy to handle, however, the PdeNHC
is ineffective with simple phenyl trimethylammonium triflate in
the Suzuki coupling, showing limited substrate scope with aryl
ammonium salts.
procedure [19]. NHCePd complexes were prepared according to
our previous procedure [20]. All other substrates and reagents were
purchased from Energy Chemical and used as received. 1H, 13C and
19F NMR spectra were recorded on a Bruker AV400 spectrometer
with chemical shift values relative to the solvent residue. HRMS
was recorded on a Bruker solarix 9.4T. HPLC was performed on an
Agilent 1200 series with 256 nm UV detector using a liquid chro-
matography column that purchased from Agela Technologies
Innoval ODS-P. Melting points were detected by microscope
melting point apparatus.
3.1.2. The synthesis of N,N,N-trimethylpyren-1-aminium
trifluoromethanesulfonate
3.1. Experimental section
Methyltriflate (0.28 mL, 2.40 mmol) was added dropwise into a
solution of N,N-dimethyl-1-pyrenamine (0.4902 g, 2 mmol) in DCM
(5 mL) in an 8 mL of vial. After the reaction was stirred overnight at
room temperature, Et2O (10 mL) was added into the mixture. The
precipitate was filtered and washed by Et2O (3 ꢁ 5 mL), and the
product was collected as a white solid.
3.1.1. General information
All manipulations were carried out under a nitrogen atmo-
sphere. All anhydrous solvents were collected from the VAC Solvent
Purifier instrument. N,N,N-trimethylpyren-1-ammonium tri-
fluoromethanesulfonate was prepared according to the following
procedure and the other aryltrimethylammonium tri-
fluoromethanesulfonates were prepared according to the literature
Yield: 0.65 g (80%). White solid. M.p. 203e204 ꢀC. 1H NMR
(400 MHz, DMSO‑d6)
d
8.92 (d, J ¼ 9.7 Hz, 1H), 8.65 (d, J ¼ 8.9 Hz,
4

H. Tang, M. Liu, M. Zhu et al.
Tetrahedron xxx (xxxx) xxx
Table 3
The Suzuki cross-coupling of arylammonium triflates with p-methylphenylboronic acid.
1H), 8.58e8.48 (m, 4H), 8.39 (d, J ¼ 8.8 Hz, 1H), 8.33 (d, J ¼ 8.8 Hz,
1H), 8.29e8.22 (m, 1H), 4.09 (s, 9H). 13C NMR (101 MHz, DMSO‑d6)
(d, J ¼ 8.3 Hz, 1H), 7.59e7.48 (m, 2H), 7.47e7.40 (m, 4H), 7.33 (d,
J ¼ 7.8 Hz, 2H), 2.48 (s, 3H). 13C NMR (100 MHz, CDCl3)
d 140.4,
d
139.5, 132.9, 131.2, 130.3, 130.0, 129.6, 128.1, 128.0, 127.5, 127.4,
138.0, 137.1, 134.0, 131.9, 130.1, 129.1, 128.4, 127.6, 127.0, 126.2, 126.1,
126.1, 125.7, 124.1, 122.8, 122.2, 119.8, 58.4. HRMS-APCI (m/z): Calcd
125.8, 125.5, 21.4. HRMS-APCI (m/z): Calcd for [MþH]þ C17H1þ5
,
for [M-OTf]þ C19H19Nþ, 260.1434; found, 260.1437.
219.1168; found, 219.1157.
3.1.3. General procedure for the Suzuki reaction
3.1.4.3. 1-(4-(tert-butyl)phenyl)naphthalene (5). Eluent (PE). White
solid. M.p. 90e91 ꢀC. 1H NMR (400 MHz, CDCl3)
THF (2.5 mL) was injected into the mixture of ammonium salts
(1 mmol), boronic acid (0.5 mmol), SIPr-PdCl2-Py (0.05 mmol) and
CsF (1 mmol) in a Schleck tube under N2 atmosphere. After stirring
for 8 h at 80 ꢀC, the mixture was concentrated via reduced pressure.
Finally, the residue was purified by flash chromatography on silica
gel with an eluent to afford the target compound.
d
7.99 (d, J ¼ 7.2 Hz,
1H), 7.92 (d, J ¼ 7.6 Hz, 1H), 7.87 (d, J ¼ 8.0 Hz, 1H), 7.58e7.50 (m,
4H), 7.50e7.41 (m, 4H), 1.44 (s, 9H). 13C NMR (100 MHz, CDCl3)
d
150.3, 140.4, 137.9, 134.0, 131.9, 129.9, 128.4, 127.6, 127.1, 126.3,
126.0, 125.8, 125.6, 125.3, 34.8, 31.6. HRMS-APCI (m/z): [MþH]þ
Calcd for C20Hþ21, 261.1638; found, 261.1633.
3.1.4. Data for products of the Suzuki reaction
3.1.4.4. methyl(4-(naphthalen-1-yl)phenyl)sulfane (6). Eluent (PE).
White solid. M.p. 91e92 ꢀC. 1H NMR (400 MHz, CDCl3)
d
7.91 (d,
J ¼ 8.0 Hz, 2H), 7.86 (d, J ¼ 8.4 Hz, 1H), 7.57e7.47 (m, 2H), 7.47e7.37
(m, 6H), 2.57 (s, 3H). 13C NMR (100 MHz, CDCl3)
139.8, 137.7, 137.6,
3.1.4.1. 1-phenylnaphthalene (3) [21]. Eluent (PE). Colorless oil. 1H
NMR (400 MHz, CDCl3):
d
7.94 (d, J ¼ 9.4 Hz, 2H), 7.89 (d, J ¼ 8.2 Hz,
1H), 7.59e7.42 (m, 9H). 13C NMR (101 MHz, CDCl3)
d
141.0, 140.5,
d
134.0, 131.7, 130.6, 128.5, 127.8, 127.0, 126.6, 126.2, 126.0, 125.9,
125.5, 16.0. HRMS-APCI (m/z): [MþH]þ Calcd for C17H15Sþ,
251.0889; found, 251.0881.
134.0, 131.8, 130.3, 128.48, 128.47, 127.8, 127.4, 127.1, þ126.24 (2C),
126.0, 125.6. HRMS-APCI (m/z): Calcd for [MþH]þ C16H13, 205.1012;
found, 205.1009.
3.1.4.2. 1-(p-tolyl)naphthalene (4) [22]. Eluent (PE). White solid.
3.1.4.5. trimethyl(4-(naphthalen-1-yl)phenyl)silane (7). Eluent (PE).
M.p. 52e53 ꢀC. 1H NMR (400 MHz, CDCl3)
d
7.98e7.90 (m, 2H), 7.87
Colorless oil. 1H NMR (400 MHz, CDCl3)
d
8.03 (d, J ¼ 7.6 Hz, 1H),
5

H. Tang, M. Liu, M. Zhu et al.
Tetrahedron xxx (xxxx) xxx
Table 4
The cross-coupling of arylboronic acid pinacol ester with 1.
Scheme 2. Suzuki cross-coupling of phenylboronic anhydride with 1.
Scheme 3. The two-step one-pot process.
Scheme 5. The proposed reaction mechanism.
7.97 (d, J ¼ 8.0 Hz, 1H), 7.92 (d, J ¼ 8.4 Hz, 1H), 7.79e7.69 (m, 2H),
7.63e7.53 (m, 4H), 7.49 (m, 2H), 0.43 (s, 9H). 13C NMR (100 MHz,
CDCl3)
d 141.3, 140.4, 139.3, 134.0, 133.4, 131.7, 129.6, 128.4, 127.8,
127.1, 126.2, 126.1, 125.9, 125.5, ꢂ0.8. HRMS-APCI (m/z): [MþH]þ
Calcd for C19H21Siþ, 277.1407; found, 277.1415.
Scheme 4. The gram-scale reaction.
3.1.4.6. 1-(4-pentylphenyl)naphthalene (8). Eluent (PE). White
solid. M.p. 77e78 ꢀC. 1H NMR (400 MHz, CDCl3)
d
8.01 (d, J ¼ 8.4 Hz,
1H), 7.95 (d, J ¼ 8.0 Hz, 1H), 7.89 (d, J ¼ 8.0 Hz, 1H), 7.62e7.51 (m,
6

H. Tang, M. Liu, M. Zhu et al.
Tetrahedron xxx (xxxx) xxx
2H), 7.51e7.44 (m, 4H), 7.36 (d, J ¼ 8.0 Hz, 2H), 2.76 (t, J ¼ 8.0 Hz,
2H), 1.86e1.71 (m, 2H), 1.51e1.42 (m, 4H), 1.05e0.97 (m, 3H). 13C
3.1.4.13. methyl
Gradient eluting: PE
66e67 ꢀC. 1H NMR (400 MHz, CDCl3)
4-(naphthalen-1-yl)benzoate
(15)
[26].
/
PE/EtOAc (40/1). White solid; M.p.
NMR (100 MHz, CDCl3))
d
142.1, 140.5, 138.2, 134.0, 131.9, 130.1,
d
8.18 (d, J ¼ 8.4 Hz, 2H), 7.92
128.4, 128.4, 127.5, 127.0, 126.3, 126.0, 125.8, 125.5, 35þ.9, 31.8, 31.4,
22.8, 14.2. HRMS-APCI (m/z): [MþH]þ Calcd for C21H23, 275.1794;
found, 275.1802.
(dd, J ¼ 10.4, 8.2 Hz, 2H), 7.86 (d, J ¼ 8.0 Hz, 1H), 7.59 (d, J ¼ 8.0 Hz,
2H), 7.57e7.53 (m, 1H), 7.53e7.49 (m, 1H), 7.48e7.42 (m, 2H), 3.99
(s, 3H). 13C NMR (100 MHz, CDCl3)
d 167.2, 145.7, 139.3, 133.9, 131.4,
130.2,129.7,129.2,128.5,128.4, 127.1, 126.5,126.1, 125.7,125. 5, 52.3.
HRMS-APCI (m/z): [MþH]þ Calcd for C18H15Oþ2 , 263.1067; found,
263.1062.
3.1.4.7. 1-(4-(trifluoromethyl)phenyl)naphthalene
Eluent (PE). White solid. M.p. 48e49 ꢀC. 1H NMR (400 MHz, CDCl3)
7.95 (t, J ¼ 8.6 Hz, 2H), 7.85 (d, J ¼ 8.4 Hz, 1H), 7.79 (d, J ¼ 8.0 Hz,
(9)
[22].
d
3.1.4.14. 1-(4-(naphthalen-1-yl)phenyl)ethan-1-one
Gradient eluting: PE PE/EtOAc (50/1). White solid. M.p.
98e99 ꢀC. 1H NMR (400 MHz, CDCl3)
(16)
[22].
2H), 7.64 (d, J ¼ 7.6 Hz, 2H), 7.61e7.52 (m, 2H), 7.51e7.46 (m, 1H),
7.44 (dd, J ¼ 6.8, 1.2 Hz, 1H). 13C NMR (100 MHz, CDCl3)
d
144.6 (d,
/
2
4JC-F ¼ 1.4 Hz), 138.9, 133.9, 131.4, 130.5, 129.6 (q, JC-F ¼ 32.3 Hz),
d
8.10 (d, J ¼ 8.4 Hz, 2H), 7.92
128.6,128.5,127.2,126.6,126.2,125.6,125.5,125.4 (q, 3JC-F ¼ 3.7 Hz),
(t, J ¼ 9.4 Hz, 2H), 7.86 (d, J ¼ 8.4 Hz, 1H), 7.61 (d, J ¼ 8.4 Hz, 2H),
7.58e7.50 (m, 2H), 7.49e7.40 (m, 2H), 2.69 (s, 3H). 13C NMR
1
124.5 (q, JC-F ¼ 270.6 Hz). 19F NMR (376 MHz, CDCl3)
d
ꢂ62.28.
HRMS-APCI (m/z): [MþH]þ Calcd for C17H12Fþ3 , 273.0886; found,
(100 MHz, CDCl3)
d 197.9, 145.9, 139.1, 136.1, 133.9, 131.3, 130.4,
128.5, 128.48, 128.46, 127.0, 126.5, 126.1, 125.7, 125. 5, 26.8. HRMS-
273.0879.
APCI (m/z): [MþH]þ Calcd for C18H15Oþ, 247.1117; found, 247.1113.
3.1.4.8. 1-(4-(trifluoromethoxy)phenyl)naphthalene
(10). Eluent
7.96 (d, J ¼ 8.0 Hz,
(PE). Colorless oil. 1H NMR (400 MHz, CDCl3)
d
3.1.4.15. N-(4-(naphthalen-1-yl)phenyl)acetamide
Gradient eluting: PE PE/EtOAc (1/1). White solid. M.p.
205e206 ꢀC. 1H NMR (400 MHz, CDCl3)
(17).
/
1H), 7.92 (d, J ¼ 8.4 Hz, 1H), 7.89 (d, J ¼ 8.0 Hz, 1H), 7.60e7.52 (m,
4H), 7.52e7.47 (m, 1H), 7.44 (dd, J ¼ 7.0, 1.4 Hz, 1H), 7.38 (d,
d
7.90 (d, J ¼ 9.2 Hz, 2H),
J ¼ 8.0 Hz, 2H). 13C NMR (100 MHz, CDCl3)
d
148.7 (q, 2JC-F ¼ 1.5 Hz),
7.85 (d, J ¼ 8.0 Hz, 1H), 7.67 (d, J ¼ 8.0 Hz, 1H), 7.54e7.46 (m, 4H),
7.45e7.37 (m, 3H), 7.23 (d, J ¼ 7.6 Hz, 1H), 2.17 (s, 3H). 13C NMR
139.6, 138.9, 134.0, 131.6, 131.5, 128.5, 128.2, 127.2, 126.5, 126.1,
125.8, 125.5, 120.91, 120.8 (q, 1JC-F ¼ 255.7 Hz). 19F NMR (376 MHz,
(100 MHz, CDCl3)
d 168.7, 141.7, 139.8, 138.0, 133.9, 131.6, 129.0,
ꢂ57.62; HRMS-APCI (m/z): [MþH]þ Calcd for C17H12F3Oþ,
128.4, 127.9, 127.0, 126.2, 126.0, 125.9, 125.4, 121.6, 119.1, 24.7.
HRMS-APCI (m/z): [MþH]þ Calcd for C18H16NOþ, 262.1226; found,
262.1221.
CDCl3)
d
289.0835; found, 289.0830.
3.1.4.9. 1-(4-fluorophenyl)naphthalene (11) [22]. Eluent (PE). White
3.1.4.16. 1-([1,10-biphenyl]-4-yl)naphthalene (18) [27]. PE. White
solid. M.p. 71e72 ꢀC. 1H NMR (400 MHz, CDCl3)
d
7.92 (dd, J ¼ 8.4,
solid. M.p. 149e150 ꢀC. 1H NMR (400 MHz, CDCl3)
d 8.01 (d,
1.2 Hz, 1H), 7.86 (t, J ¼ 8.8 Hz, 2H), 7.57e7.50 (m, 1H), 7.54e7.46 (m,
1H), 7.50e7.40 (m, 3H), 7.40 (dd, J ¼ 7.2, 1.2 Hz, 1H), 7.23e7.15 (m,
J ¼ 8.8 Hz, 1H), 7.94 (d, J ¼ 7.6 Hz, 1H), 7.90 (d, J ¼ 8.0 Hz, 1H),
7.79e7.66 (m, 4H), 7.64e7.45 (m, 8H), 7.43e7.38 (m, 1H). 13C NMR
2H). 13C NMR (100 MHz, CDCl3)
d
162.4 (d, 1JC-F ¼ 244.9 Hz), 139.3,
(100 MHz, CDCl3)
d 141.0, 140.3, 134.0, 139.9, 134.0, 131.8, 130.6,
136.8 (d, 4JC-F ¼ 3.3 Hz), 134.0, 131.8, 131.7 (d, 3JC-F ¼ 7.9 Hz), 128.5,
129.0, 128.5, 127.9, 127.5, 127.3, 127.1, 127.1, 126þ.2, 126.2, 126.0, 125.
6. HRMS-APCI (m/z): [MþH]þ Calcd for C22H17, 281.1325; found,
281.1329.
128.0, 127.2, 126.3, 126.0, 125.9, 125.5, 115.3 (d, 2JC-F ¼ 21.2 Hz). 19
F
NMR (376 MHz, CDCl3)
d
ꢂ115.47; HRMS-APCI (m/z): [MþH]þ Calcd
for C16H12Fþ, 223.0981; found, 223.0985.
3.1.4.17. 1-(4-(benzyloxy)phenyl)naphthalene
eluting: PE / PE/EtOAc (40/1). Colorless oil. 1H NMR (400 MHz,
CDCl3)
7.93 (dd, J ¼ 13.4, 8.2 Hz, 2H), 7.85 (d, J ¼ 8.4 Hz, 1H),
(19). Gradient
3.1.4.10. 1-(4-chlorophenyl)naphthalene (12) [23]. Eluent (PE).
Colorless oil. 1H NMR (400 MHz, CDCl3)
7.92 (d, J ¼ 8.0 Hz, 1H),
d
d
7.88e7.83 (m, 2H), 7.56e7.52 (m, 1H), 7.52e7.42 (m, 6H), 7.40 (dd,
7.57e7.48 (m, 4H), 7.47e7.40 (m, 6H), 7.40e7.35 (m, 1H), 7.12 (d,
J ¼ 7.2, 1.2 Hz, 1H). 13C NMR (100 MHz, CDCl3)
d 139.3, 139.1, 133.9,
J ¼ 8.8 Hz, 2H), 5.17 (s, 2H). 13C NMR (100 MHz, CDCl3)
d 158.3,
133.5, 131.6, 131.5, 128.6, 128.5, 128.1, 127.1, 126.4,126.1, 126.0,125.8,
125.5. HRMS-APCI (m/z): [MþH]þ Calcd for C16H12Clþ, 239.0622;
found, 239.0622.
140.0, 137.2, 134.0, 133.6, 132.0, 131.3, 128. 8, 128.4, 128.2, 127.7,
127.5, 127.1, 126.2, 126.1, 125.8, 125.5, 114. 8, 70.3. HRMS-APCI (m/z):
[MþH]þ Calcd for C23H19Oþ, 311.1430; found, 311.1427.
3.1.4.11. 4-(naphthalen-1-yl)benzonitrile (13) [24]. Gradient eluting
(PE / PE/EtOAc (40/1)). White solid; M.p. 76e77 ꢀC; 1H NMR
3.1.4.18. 1-(2-methoxyphenyl)naphthalene
eluting: PE / PE/EtOAc (100/1). White solid. M.p. 98e99 ꢀC. 1H
NMR (400 MHz, CDCl3)
(20)
[28]. Gradient
(400 MHz, CDCl3)
d
7.93 (d, J ¼ 7.6 Hz, 2H), 7.79 (d, J ¼ 8.3 Hz, 3H),
d
7.91 (t, J ¼ 9.0 Hz, 2H), 7.62 (d, J ¼ 8.8 Hz,
7.61 (d, J ¼ 8.2 Hz, 2H), 7.60e7.50 (m, 2H), 7.52e7.43 (m, 1H), 7.41
1H), 7.56 (t, J ¼ 7.6 Hz, 1H), 7.53e7.38 (m, 4H), 7.33 (dd, J ¼ 7.4,
(dd, J ¼ 7.1, 1.2 Hz, 1H). 13C NMR (100 MHz, CDCl3)
d 145.8, 138.3,
1.8 Hz, 1H), 7.16e7.02 (m, 2H), 3.72 (s, 3H). 13C NMR (100 MHz,
133.9, 132.2, 131.1, 130.9, 128.9, 128.7, 127.1, 126.8, 126.3, 125.4,
125.3, 119.0, 111.3. HRMS-APCI (m/z): [MþH]þ Calcd for C17H12Nþ,
230.0964; found, 230.0960.
CDCl3)
d 157.4, 137.1, 133.6, 132.3, 132.1, 129.7, 129.1, 128.3, 127.8,
127.4, 126.6, 125.8, 125.7, 125.5, 120.7, 111.1, 55.7. HRMS-APCI (m/z):
[MþH]þ Calcd for C17H15Oþ, 235.1117; found, 235.1120.
3.1.4.12. 1-(4-nitrophenyl)naphthalene (14) [25]. Gradient eluting:
PE / PE/EtOAc (10/1); White solid. M.p. 131e132 ꢀC. 1H NMR
3.1.4.19. 1-(3-methoxyphenyl)naphthalene
eluting: PE / PE/EtOAc (100/1). Colorless oil. 1H NMR (400 MHz,
CDCl3)
(21)
[29]. Gradient
(400 MHz, CDCl3)
d
8.40e8.32 (m, 2H), 7.95 (dd, J ¼ 8.0, 3.2 Hz, 2H),
d
7.99 (d, J ¼ 8.8 Hz, 1H), 7.94 (d, J ¼ 8.4 Hz, 1H), 7.90 (d,
7.80 (d, J ¼ 8.0 Hz, 1H), 7.71e7.64 (m, 2H), 7.61e7.50 (m, 2H),
J ¼ 8.4 Hz, 1H), 7.60e7.49 (m, 2H), 7.52e7.40 (m, 3H), 7.16e7.08 (m,
7.54e7.44 (m, 1H), 7.44 (dd, J ¼ 6.8, 1.2 Hz, 1H); 13C NMR (100 MHz,
2H), 7.06e6.99 (m, 1H), 3.89 (s, 3H); 13C NMR (100 MHz, CDCl3)
CDCl3)
d
147. 8, 147.3, 137.9, 133.9, 131.1, 131.0, 129.1, 128.7, 127.2,
d 159.6, 142.3, 140.2, 133.9, 131.7, 129.4, 128.4, 127.8, 126.9, 126.2,
126.9, 126.4, 125.4, 125.3, 123.7; HRMS-APCI (m/z): [MþH]þ Calcd
126.2, 125.9, 125.5, 122.7, 115.8, 113.0, 55.4; HRMS-APCI (m/z):
for C16H12NOþ2 , 250.0863; found, 250.0859.
[MþH]þ Calcd for C17H15Oþ, 235.1117; found, 235.1119.
7

H. Tang, M. Liu, M. Zhu et al.
Tetrahedron xxx (xxxx) xxx
3.1.4.20. 1-(4-methoxyphenyl)naphthalene
(22)
[22]. Gradient
(d, J ¼ 8.4 Hz,1H), 7.62e7.48 (m, 5H), 7.44 (dd, J ¼ 7.0,1.4 Hz,1H). 13
C
eluting: PE / PE/EtOAc (100/1). White solid; M.p. 115e116 ꢀC; 1H
NMR (100 MHz, CDCl3) d 151.4, 147.7, 136.6, 133.9, 130.6, 129.7,
NMR (400 MHz, CDCl3)
7.55e7.47 (m, 2H), 7.47e7.40 (m, 4H), 7.09e7.01 (m, 2H), 3.91 (s,
3H); 13C NMR (100 MHz, CDCl3)
159.1, 140.1, 134.0, 133.3, 132.0,
d
7.96e7.89 (m, 2H), 7.85 (d, J ¼ 8.0 Hz, 1H),
128.8, 127.3, 127.2, 126.6, 125.9, 125.5, 124.9. HRMS-APCI (m/z):
[MþH]þ Calcd for C15H12Nþ, 206.0964; found, 193.1018.
d
131.3, 128.4, 127.5, 127.4, 126.2, 126.1, 125.8, 125.5, 113.9, 55.5;
HRMS-APCI (m/z): [MþH]þ Calcd for C17H15Oþ, 235.1117; found,
235.1122.
3.1.4.28. 1-(p-tolyl)-3a1,5a1-dihydropyrene (30). PE. White solid.
M.p. 70e71 ꢀC. 1H NMR (400 MHz, CDCl3)
d 8.25e8.15 (m, 4H), 8.10
(s, 1H), 8.01 (dd, J ¼ 15, 7.8 Hz, 3H), 7.55 (d, J ¼ 8.0 Hz, 2H), 7.40 (d,
J ¼ 8.0 Hz, 2H), 2.52 (s, 3H). 13C NMR (100 MHz, CDCl3)
d 138.4,
3.1.4.21. 1,10-binaphthalene (23) [29]. PE. White solid. M.p.
137.9, 137.1, 131.6, 131.1, 130.6, 130.6, 129.2, 128.7, 127.8, 127.6, 127.5,
127.4, 126.1, 125.5, 125.2, 125.12, 125.08, 124.9, 124.8, 21.4. HRMS-
APCI (m/z): [MþH]þ Calcd for C23H1þ7, 293.3885; found, 293.3879.
159e160 ꢀC; 1H NMR (400 MHz, CDCl3)
d
7.98 (dd, J ¼ 8.4, 3.6 Hz,
4H), 7.66e7.58 (m, 2H), 7.57e7.46 (m, 4H), 7.44 (d, J ¼ 7.2 Hz, 2H),
7.35e7.28 (m, 2H); 13C NMR (100 MHz, CDCl3)
138.6, 133.7, 133.0,
d
128.3, 128.0, 128.0, 126.7, 126.1, 125.9, 125.5; HRMS-APCI (m/z):
3.1.4.29. 7-methoxy-1-(p-tolyl)naphthalene (31) [31]. Gradient
eluting: PE / PE/EtOAc (100/1). White solid. M.p. 90e91 ꢀC. 1H
[MþH]þ Calcd for C20H1þ5, 255.1168; found, 255.1163.
NMR (400 MHz, CDCl3)
d
7.85 (d, J ¼ 8.8 Hz, 1H), 7.84e7.79 (m, 1H),
3.1.4.22. (E)-1-styrylnaphthalene (24). Gradient eluting: PE / PE/
EtOAc (100/1). White solid. M.p. 199e200 ꢀC; 1H NMR (400 MHz,
7.48 (d, J ¼ 8.0 Hz, 2H), 7.45e7.41 (m, 2H), 7.39e7.32 (m, 3H), 7.23
(dd, J ¼ 9.0, 2.6 Hz,1H), 3.82 (s, 3H), 2.51 (s, 3H). 13C NMR (100 MHz,
CDCl3)
d
8.26 (d, J ¼ 7.2 Hz, 1H), 7.97e7.88 (m, 2H), 7.84 (d,
CDCl3) d 157.9, 139.1, 138.2, 136.9, 132.9, 129.91, 129.86, 129.5, 129.2,
J ¼ 8.0 Hz, 1H), 7.78 (d, J ¼ 7.2 Hz, 1H), 7.64 (d, J ¼ 7.2 Hz, 2H),
127.6, 127.3, 123.3, 118.4, 104.7, 55.3, 21.4. HRMS-APCI (m/z):
7.61e7.49 (m, 3H), 7.44 (t, J ¼ 7.4 Hz, 2H), 7.34 (t, J ¼ 7.3 Hz, 1H), 7.19
[MþH]þ Calcd for C18H17Oþ, 249.1274; found, 249.1268.
(d, J ¼ 16.0 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d 137.8, 135.2, 133.9,
131.9, 131.5, 128.9, 128.8, 128.2, 127.9, 126.8, 126.2, 127.0, 126þ.0,
125.8, 123.9, 123.8; HRMS-APCI (m/z): [MþH]þ Calcd for C18H15
,
3.1.4.30. 5-(p-tolyl)-1-naphthonitrile (32). Gradient eluting: PE /
PE/EtOAc (40/1). Colorless oil. 1H NMR (400 MHz, CDCl3)
d 8.27 (d,
231.1168; found, 231.1171.
J ¼ 8.4 Hz, 1H), 8.18 (d, J ¼ 8.8 Hz, 1H), 7.92 (dd, J ¼ 6.8, 1.2 Hz, 1H),
7.73 (dd, J ¼ 8.4, 7.2 Hz, 1H), 7.55 (dd, J ¼ 7.2, 1.2 Hz, 1H), 7.46 (dd,
J ¼ 8.6, 7.0 Hz, 1H), 7.38e7.30 (m, 4H), 2.47 (s, 3H). 13C NMR
3.1.4.23. 4-(naphthalen-1-yl)dibenzo[b,d]furan (25). PE. White
solid. M.p. 105e106 ꢀC; 1H NMR (400 MHz, CDCl3)
8.06 (t,
d
(100 MHz, CDCl3)
d 141.4, 137.7, 136.7, 132.9, 132.7, 131.8, 131.6,
J ¼ 7.8 Hz, 2H), 8.02e7.94 (m, 2H), 7.73 (d, J ¼ 8.4 Hz, 1H), 7.70e7.61
(m, 2H), 7.59e7.48 (m, 3H), 7.48e7.34 (m, 4H); 13C NMR (100 MHz,
130.0, 129.3, 128.6, 128.2, 125.0, 124.6, 118.2, 110.5, 21.4. HRMS-APCI
(m/z): [MþH]þ Calcd for C18H14Nþ, 244.1121; found, 244.1116.
CDCl3)
d 156.4, 154.3, 134.7, 133.9, 132.0, 129.4, 128.6, 128.5, 128.0,
127.3, 126.3, 126.3, 126.0, 125. 6, 125.1, 124.6, 124.5, 123.0, 122.9,
120.8, 120.1, 112.1; HRMS-APCI (m/z): [MþH]þ Calcd for C22H15Oþ,
295.1117; found, 295.1113.
3.1.4.31. 2-(p-tolyl)pyridine (33) [28]. Gradient eluting: PE/EtOAc
(20/1) / PE/EtOAc (5/1). White solid; M.p. 107e108 ꢀC; 1H NMR
(400 MHz, CDCl3)
d
8.73e8.65 (m, 1H), 7.91 (d, J ¼ 8.4 Hz, 2H),
3.1.4.24. 4-(naphthalen-1-yl)dibenzo[b,d]thiophene (26). PE. White
7.77e7.66 (m, 2H), 7.29 (d, J ¼ 8.0 Hz, 2H), 7.23e7.15 (m, 1H), 2.41 (s,
solid. Mp: 118e119 ꢀC; 1H NMR (400 MHz, CDCl3)
d 8.25 (t,
3H). 13C NMR (100 MHz, CDCl3)
d 157.5, 149.6, 139.1, 136.8, 136.6,
129.6, 126.9, 121.9, 120.46, 21.4. HRMS-APCI (m/z): [MþH]þ Calcd
J ¼ 8.0 Hz, 2H), 7.98 (dd, J ¼ 8.0, 4.4 Hz, 2H), 7.74 (d, J ¼ 8.0 Hz, 1H),
7.70e7.58 (m, 4H), 7.56e7.41 (m, 4H), 7.38 (t, J ¼ 7.8 Hz, 1H); 13C
for C12H12Nþ, 170.0964; found, 170.0959.
NMR (100 MHz, CDCl3)
d 140.9, 139.9, 138.3, 136.0, 135.9, 135.7,
134.0, 131.4, 128.7, 128.5, 128.4, 127.1, 126.9, 126.3, 126.2, 126.1,
125.6, 124.8, 124.5, 122.9, 121.9, 120.8; HRMS-APCI (m/z): [MþH]þ
Calcd for C22H15Sþ, 311.0889; found, 311.0883.
3.1.4.32. 1-benzyl-4-methylbenzene (35) [15b]. Eluent: PE. Colorless
oil; 1H NMR (400 MHz, CDCl3)
d
7.34e7.25 (m, 2H), 7.25e7.17 (m,
3H), 7.11 (s, 4H), 3.97 (s, 2H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3)
d
141.6, 138.2, 135.7, 129.3, 129.0, 128.9, 128.6, 126.1, 41.7, 21.1;
3.1.4.25. 2-(naphthalen-1-yl)thiophene (27) [30]. PE. Colorless oil.
HRMS-APCI (m/z): [MþH]þ Calcd for C14H1þ5, 183.1168; found,
1H NMR (400 MHz, CDCl3)
d 8.33e8.17 (m, 1H), 7.97e7.90 (m, 1H),
183.1172.
7.89 (d, J ¼ 8.0 Hz, 1H), 7.62 (d, J ¼ 6.8 Hz, 1H), 7.58e7.49 (m, 3H),
7.47 (dd, J ¼ 5.2, 1.2 Hz, 1H), 7.30 (d, J ¼ 3.2 Hz, 1H), 7.23 (dd, J ¼ 5.2,
3.6 Hz, 1H). 13C NMR (100 MHz, CDCl3)
d 141.9, 134.0, 132.6, 132.0,
3.1.4.33. 4-(naphthalen-1-yl)benzaldehyde
eluting: PE / PE/EtOAc (40/1). White solid; M.p. 67e68 ꢀC; 1H
NMR (400 MHz, CDCl3)
(43)
[29]. Gradient
128.5, 128.5, 128.3, 127.5, 127.4, 126.6, 126.1, 125.9, 125.8, 125.4.
HRMS-APCI (m/z): [MþH]þ Calcd for C14H11Sþ, 211.0576; found,
211.0569.
d
10.13 (s, 1H), 8.02 (d, J ¼ 8.2 Hz, 2H), 7.93
(t, J ¼ 8.0 Hz, 2H), 7.85 (d, J ¼ 8.4 Hz, 1H), 7.68 (d, J ¼ 8.2 Hz, 2H),
7.60e7.51 (m, 2H), 7.50e7.43 (m, 2H). 13C NMR (101 MHz, CDCl3)
d
157.3, 137.0, 133.5, 132.2, 132.0, 130.3, 129.6, 129.1, 128.2, 127.7,
3.1.4.26. 5-(naphthalen-1-yl)benzo[d][1,3]dioxole
Gradient eluting: PE / PE/EtOAc (100/1). Colorless oil. 1H NMR
(400 MHz, CDCl3)
7.98 (d, J ¼ 8.4 Hz, 1H), 7.92 (d, J ¼ 8.0 Hz, 1H),
7.87 (d, J ¼ 8.0 Hz, 1H), 7.57e7.47 (m, 2H), 7.51e7.39 (m, 2H),
7.04e6.93 (m, 3H), 6.06 (s, 2H). 13C NMR (100 MHz, CDCl3)
147.6,
(28)
[24].
127.4, 126.5, 125.7, 125.6, 125.4, 120.6, 111.7, 55.6. HRMS-APCI (m/z):
[MþH]þ Calcd for C17H13Oþ, 233.0966; found, 233.0955.
d
d
3.1.4.34. 2-(naphthalen-1-yl)furan (49) [31]. PE. Colorless oil. 1H
147.0, 140.0, 134.8, 134.0, 131.9, 128.4, 127.7, 127.0, 126.13, 126.11,
125.9, 125.5, 123.6, 110.8, 108.4, 101.2. HRMS-APCI (m/z): [MþH]þ
Calcd for C17H13Oþ2 , 249.0910; found, 249.0915.
NMR (400 MHz, CDCl3)
d
8.49 (d, J ¼ 7.2 Hz, 1H), 7.98e7.91 (m, 1H),
7.89 (d, J ¼ 8.4 Hz, 1H), 7.80 (dd, J ¼ 7.2, 1.2 Hz, 1H), 7.68 (d,
J ¼ 1.6 Hz, 1H), 7.64e7.53 (m, 3H), 6.79 (d, J ¼ 3.2 Hz, 1H), 6.64 (dd,
J ¼ 3.2, 1.6 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d 153.6, 142.5, 134.1,
3.1.4.27. 4-(naphthalen-1-yl)pyridine (29) [30]. Gradient eluting:
DCM / DCM/MeOH (50/1). White solid. M.p. 94e95 ꢀC. 1H NMR
130.5, 128.7, 128. 7, 128.6, 126.7, 126.3, 126.0, 125. 7, 125.4, 111.5,
109.3. HRMS-APCI (m/z): [MþH]þ Calcd for C14H11Oþ, 195.0810;
found, 195.0801.
(400 MHz, CDCl3)
d
8.76 (d, J ¼ 6.4 Hz, 2H), 8.00e7.91 (m, 2H), 7.82
8

H. Tang, M. Liu, M. Zhu et al.
Tetrahedron xxx (xxxx) xxx
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Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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Acknowledgement
We are grateful to the National Natural Science Foundation of
China (22171110 and 21571087) for the financial support.
Appendix A. Supplementary data
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