Synthesis of naphthyl-substituted terminal olefins via Pd-Catalyzed one-pot coupling of acetylnaphthalene, N-Tosylhydrazide with aryl halide

Article abstract of DOI:10.1016/j.tet.2017.09.052

In this study, a one-pot two-step Pd-catalyzed reductive eliminate between acetyl naphthalene derivatives, tosylhydrazide, and aryl halide, affording substituted 1(or 2)-(1-phenylvinyl)naphthalene in moderate-to-excellent yields, was reported. Notably, so

Full text of DOI:10.1016/j.tet.2017.09.052

Accepted Manuscript
Synthesis of naphthyl-substituted terminal olefins via Pd-Catalyzed one-pot coupling
of acetylnaphthalene, N-Tosylhydrazide with aryl halide
Xu Shen, Ping Liu, Yan Liu, Bin Dai
PII:
S0040-4020(17)31008-6
10.1016/j.tet.2017.09.052
TET 29003
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 22 June 2017
Revised Date: 14 August 2017
Accepted Date: 30 September 2017
Please cite this article as: Shen X, Liu P, Liu Y, Dai B, Synthesis of naphthyl-substituted terminal olefins
via Pd-Catalyzed one-pot coupling of acetylnaphthalene, N-Tosylhydrazide with aryl halide, Tetrahedron
(2017), doi: 10.1016/j.tet.2017.09.052.
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Synthesis of Naphthyl-Substituted Terminal Olefins
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via Pd-Catalyzed One-Pot Coupling of
Acetylnaphthalene, N-Tosylhydrazide with Aryl
Halide
Xu Shena, Ping Liua, *, Yan Liua, *, and Bin Daia
aSchool of Chemistry and Chemical Engineering/Key Laboratory for Green Processing of Chemical Engineering of
Xinjiang Bingtuan，Shihezi University, Shihezi 832003, China
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Graphical Abstract
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Synthesis of Naphthyl-Substituted Terminal Olefins
Leave this area blank for abstract info.
via Pd-Catalyzed One-Pot Coupling of
Acetylnaphthalene, N-Tosylhydrazide with Aryl
Halide
Xu Shena, Ping Liua, *, Yan Liua, *, and Bin Daia
aSchool of Chemistry and Chemical Engineering/Key Laboratory for Green Processing of Chemical Engineering of
Xinjiang Bingtuan，Shihezi University, Shihezi 832003, China
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Tetrahedron
journal homepage: www.elsevier.com
Synthesis of Naphthyl-Substituted Terminal Olefins via Pd-Catalyzed One-Pot
Coupling of Acetylnaphthalene, N-Tosylhydrazide with Aryl Halide
Xu Shena, Ping Liua, *, Yan Liua, *, and Bin Daia
aSchool of Chemistry and Chemical Engineering/Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan
Shihezi 832003, China
，Shihezi University,
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
In this study, an one-pot two-step Pd-catalyzed reductive eliminate between acetyl naphthalene
derivatives, tosylhydrazide, and aryl halide, affording substituted 1(or 2)-(1-
phenylvinyl)naphthalene in moderate-to-excellent yields, was reported. Notably, solvent played
a crucial role in the coupling of 1-acetyl naphthalene derivatives (toluene) or 2-acetyl
naphthalene derivatives (1, 4-dioxane) as starting materials. Meanwhile, the scope of this one-
pot coupling reaction was extended to 1(or 2)-naphthaldehyde substrates. Importantly, the
catalytic system can be employed on a wide variety of substrates with good functional group
tolerance. This protocol could also be particularly useful for the synthesis of olefins-substituents
hydroxyl compounds.
Available online
Keywords:
Acetyl naphthalene
Pd-catalyzed
2009 Elsevier Ltd. All rights reserved
.
N-tosylhydrazones
aryl halide
1. Introduction
Pd(0)-catalyzed cross-coupling reactions of diazirines with aryl
halides, affording a series of substituted olefins[19]. In 2015, Chen
et al. reported olefin preparation via the palladium-catalyzed
oxidative de-azotative and de-sulfitative internal cross-coupling
Substituted olefins are one of the versatile functional groups
and intermediates in organic synthesis owing to their unique
reaction properties[1]. Among the known synthetic routes to
obtain the diarylethylene skeleton, the Mizoroki–Heck and the
Wittig reactions are the most popular methods[2]. In addition,
of sulfonylhydrazones[20]. Based on our previous reports[21]
,
herein, we envisioned a new approach for the synthesis of
naphthyl-substituted terminal olefins by Pd-catalyzed one-pot
coupling of acetylnaphthalene and tosylhydrazide with aryl
halides(Scheme 1).
other related synthetic protocols were also reported[3-11]
.
Naphthyl-substituted olefins as an important member of this
family have attracted considerable attention[12]. Very limited
methods, especially those involving the naphthyl-substituted
terminal olefins, have been developed for the synthesis of these
type of products[13]. Thus, new methodologies for the efficient
synthesis of this type of skeleton are highly desired. Transition-
metal catalyzed cross-coupling reactions have been developed as
an efficient approach for the synthesis of olefins[14]. However,
these methods are often limited by sensitive/or expensive
organometallic reagents, catalysts, and ligands, narrow substrate
scopes, and so on.
Previous work:
H3C
Ar
H3C
Ar
Ar-B(OH)2
110 o
Ar-B(OH)2
O
TsNHNH2
TsNHNH2
CH3
110 o
C
Dioxane
C
Toluene
This work:
H2C
Ar
H3C
Ar
Pd(PPh3
Ar-Br
)
4
Pd(PPh3)4
Ar-Br
O
TsNHNH2
TsNHNH2
CH2
Toluene
Dioxane
90 o
C
110 o
C
Scheme 1. One-pot coupling of acetylnaphthalene, TsNHNH2
with aryl halide or arylboronic acids.
Recently, N-tosylhydrazones proven to be highly versatile
synthetic intermediates have attracted considerable interest in a
variety of research fields[15]. In 2007, Barluenga et al. reported a
palladium-catalyzed coupling reaction between N-tosylhydrazone
2. Results and Discussion
2.1. Optimization of the reaction conditions
and aryl halides for the preparation of polysubstituted olefins[16]
.
Initially, β-acetylnaphthalene (0.5 mmol) and 4-bromotoluene
(1.0 mmol) were used as the reactants for model reaction in the
presence of tosylhydrazide (1.5 equiv) using Pd(PPh3)4 (5 mol%)
as the catalyst, LiOtBu (1.0 mmol) as the base, and 1,4-dioxane
as the solvent, affording 80% yield of the desired product. The
same reaction using Pd(OAc)2/PCy3ꢀHBF4 as the catalyst instead
of Pd(PPh3)4 afforded 66% yield of the desired product. Further,
Subsequently, Barluenga’s group and other groups investigated a
series of palladium-catalyzed coupling reactions of different N-
tosylhydrazone substrates with aryl halides to synthesize various
substituted olefins[17]. In 2010, Wang et al. reported the Pd-
catalyzed reaction of N-tosylhydrazones and arylboronic acids,
providing olefin derivatives[18]. Meanwhile, they also reported the

2
Tetrahedron
the effects of bases on the reaction were investigated (Table 1).
Using the β-acetylnaphthalene N-tosylhydrazone as substrates
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K2CO3, K3PO4, KOH, and Cs2CO3 gave lower yields in the range
40–72% (Entries 2–6). Moreover, solvent screening showed
dioxane to the best solvent (Entries 7–10). In the presence of
nitrogen (N2) atmosphere, the product was obtained in 78% yield
(Entry 10). The reaction proceeded more efficiently at high
temperatures, and high yield was obtained when the temperature
was increased up to 110 °C (Entry 11). Based on these
observations, the optimized reaction conditions are as follows:
dioxane as solvent, temperature 80 °C and reaction time(T2) 6 h
at 90 °C; and LiOtBu as base.
helped to improve the yields in some cases.
Table 2. One-pot reductive eliminating of β-acetylnaphthalene,
tosylhydrazide, and aryl halide [a]
.
Table 1. Optimized reaction conditions[a]
Entry
1
2
3
4
5
6
7
8
Base
Solvent
T2(°C)
90
90
90
90
90
90
90
90
Yield (%)[b]
LiOtBu
K2CO3
K3PO4
KOH
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
80/66[c]
56
66
40
72
49
58
72
70
79
Cs2CO3
LiOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
Toluene
CH3CN
DMF
DMSO
Dioxane
Dioxane
9
10
11[d]
90
110
90
78
[a] Reaction conditions: (i) 0.5 mmol β-acetylnaphthalene,
0.75 mmol tosylhydrazide, 3 mL solvent, 80 °C, 2 h; (ii) 1.0
mmol 4-bromotoluene, 2.0 equivalents base, 5 mol% catalyst, 90-
110 ºC, 6 h.
[b] Isolated yield.
[a] Reaction conditions: (i) 0.5 mmol β-acetylnaphthalene,
0.75 mmol tosylhydrazide, 3 mL dioxane, 80 °C(T1), 2 h; (ii) 1.0
mmol aryl bromide, 2.0 equivalents LiOtBu, 5mol% Pd(PPh3)4,
90 ºC(T2), 6 h. The yields of isolated products are given;
[c] 5 mol% Pd(OAc)2 and 10 mol% PCy3•HBF4 as catalyst.
[d] N2 protection.
2.2. Scope and limitations of substrates
[b] β-Acetylnaphthalene N-tosylhydrazone was used;
[c] t = 2 h.
With the optimized reaction conditions in hand, the scope of
the reaction was then studied, and the results are depicted in
Table 2. The electronic and steric nature of the substituents on
the aryl halides did not significantly affect the reaction. The
reaction worked well with both electron-donating substituents,
such as a methoxy group (2b, 2f, and 2i) with similar results in
different positions, and with electron-withdrawing substituents
such as chlorine (2c, 2g, 2j) and bromine (2d, 2h, and 2k)
groups, and these substituents were tolerated in the reaction
conditions, which is advantageous for further transformations.
However, the reaction of 2e with a powerful electron-donating
hydroxyl substituent at the para-position was relatively
complicated and sluggish, affording only 16% of the desired
product. The transformation worked for the substrate bearing CF3
Scheme 2. The effect of solvent and temperature on the reaction
of α-acetyl naphthalene, TsNHNH2, with 4-bromotoluene.
Then, the scope of the substrates was expanded to α-
acetylnaphthalene; however, the above-mentioned catalytic
system was not found to be suitable for α-acetylnaphthalene.
Therefore, reoptimization of the reaction conditions of α-
acetylnaphthalene susbstrate was necessary(Scheme 2).
Subsequently, α-acetylnaphthalene and 4-bromotoluene were
selected as the substrates to further investigate the effects of other
factors, including solvents and reaction temperature. Solvent is
an important factor in the catalysis. When toluene was used as
the primary solvent, 58% yield of the desired product 3a was
obtained. 1,4-Dioxane gave relatively low yields of the reaction
products. Meanwhile, the reaction proceeded more efficiently at
(2l)
substituent;
2-bromonaphthalene
(2p)
and
1-
bromonaphthalene (2o) also exhibited excellent substrate,
affording 82% and 76% overall yields of the desired products,
respectively. Identically, halogenated aromatic heterocycles such
as 3-bromothiophene (2m) and 3-bromopyridine (2n) also
showed moderate yields of 57% and 64%, respectively. Notably,
when 5-bromo-1,2,3-trimethoxybenzene was used as a reaction
partner, the desired product (2q) was obtained in 86% yield. The
coupling reaction of 6-OMe substituted β-acetylnaphthalene and
1-bromo-2-fluorobenzene also led to the product 2r in 72% yield.

3
high-temperature, i.e., when the temperature was increased up to
110 °C, the highest yield up to 76% was obtained.
N-tosylhydrazone as substrates helped to improve the yields in
some cases.
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Table 3. One-pot reductive eliminating of α-acetylnaphthalene,
To demonstrate the practical usefulness of this reaction, a
gram-scale experiment was carried out with β-acetylnaphthalene
1a and 5-bromo-1, 2, 3-trimethoxybenzene. The gram-scale
experiment gave comparable result (Scheme 3).
tosylhydrazide, and aryl halide [a]
.
Scheme 3. A gram-scale synthesis of products 2q.
3. Conclusions
To summarize, a simple and efficient method for the synthesis
of olefins via Pd-catalyzed reductive elimination of aryl halide
with N-tosylhydrazones in situ was developed, affording the
corresponding target molecules in moderate to excellent yields.
Moreover, the desired N-tosylhydrazones were not isolated, and
the reaction was carried out in two steps one-pot directly to form
the olefins derivatives. Potential substrates for this reaction are
diverse, exhibiting
a superior functional-group tolerance.
Notably, this protocol was also found to be suitable for the
synthesis of olefins-substituted hydroxyl compounds. Further
studies to explore this reaction system to other related reactions
are currently underway in our laboratory.
4. Experimental Section
4.1. Materials and instruments
Chemicals were obtained commercially and used as received.
NMR spectra were recorded on a Bruker DPX–400 spectrometer
using TMS as the internal standard. EI–Mass spectrum was
measured on a LC/Q–TOF MS (Micromass, England) All
products were isolated by short chromatography on a silica gel
(200–300 mesh) column using petroleum ether (60–90 °C),
unless otherwise noted. Acetylnaphthalene and its derivatives,
and aryl bromides were of analytical grade quality, purchased
from Adamas-beta Pharmaceuticals, Inc.
[a] Reaction conditions: (i) 0.5 mmol α-acetylnaphthalene, 0.75
mmol tosylhydrazide, 3 mL toluene, 80 °C, 2 h; (ii) 1.0 mmol
aryl bromide, 2.0 equivalents LiOtBu, 5 mol% Pd(PPh3)4, 110 ºC,
6 h;
[b] α-Acetylnaphthalene N-tosylhydrazone was used.
The scope of substrates was then investigated with this
catalytic system under the optimized reaction conditions. As
listed in Table 3, in general, most of the aryl halides reacted
smoothly, affording the desired products in moderate to excellent
yields. Seemingly, electron-donating group have a significant
effect on the reaction. For example, aryl bromides with a
methoxy group afforded the products 3b and 3e in 82% and 84%
yield, respectively. Furthermore, naphthyl bromides, 3g and 3i,
also afforded 67% and 56% yields, respectively. In addition,
halogenated aromatic heterocycles such as 3-bromopyridine (3j)
and 3-bromothiophene (3k) also reacted successfully, furnishing
the desired products in 78% and 67% yields, respectively;
however, aryl bromides (3c, 3d, 3f–3i) such as 1, 2-
dibromobenzene, 1,4-dibromobenzene, 1,3-dibromobenzene, 4-
4.2. General procedure for Pd-catalyzed one-pot two-step
reaction of acetylnaphthalene, N-tosylhydrazide with aryl halide
Acetylnaphthalene (0.5 mmol) and tosylhydrazide (0.75 mmol)
were taken in 3 mL of solvent in in a reaction tube, and the
resulting reaction mixture was stirred at 80 ºC for 2 h. Lithium
tert-butoxide (1.5 mmol) and appropriate aryl bromide (1.0 mmol)
were added to the reaction mixture. The system was heated under
reflux at 90 ºC for 6 h with stirring. After the completion of the
reaction, the reaction mixture was allowed to cool to room
temperature. Dichloromethane and a saturated solution of
NaHCO3 were added to the cooled reaction mixture, and the
layers were separated. The aqueous phase was re-extracted thrice
with dichloromethane. The combined organic extract was washed
with a saturated solution of NaHCO3, followed by brine, dried
over anhydrous MgSO4, and filtered. The solvent was removed
under reduced pressure, and the crude products thus obtained
were purified by column chromatography on silica gel.
bromochlorobenzene,
3-bromochlorobenzen,
2-
bromochlorobenzene with electron-withdrawing groups afforded
the corresponding products in low to moderate yields. The
coupling of 1-bromonaphthalene and 2-bromonaphthalene as
substrates also led to the products 3k and 3l in 67% and 56%
yields, respectively. It is particularly gratifying that the reactions
of α-acetylnaphthalene derivatives containing electron-donating
group such as methoxyl and methyl substituents exclusively
afforded the corresponding products 3o-3q in the yields of 80-
87%, and the reaction with 4-F substituent also furnished the
desired product in 76% yield(3n). Using the α-acetylnaphthalene
4.3. 2-(1-(4-chlorophenyl)vinyl)naphthalene [2c]
1
Colorless oil, H NMR (400 MHz, CDCl3) δ 7.88 – 7.71 (m,
4H), 7.53 – 7.42 (m, 3H), 7.32 (s, 4H), 5.60 (s, 1H), 5.53 (s, 1H).
13C NMR (101 MHz, CDCl3) δ 149.11, 140.11, 138.53, 133.83,
133.39, 133.15, 129.81, 128.57, 128.31, 127.99, 127.75, 127.43,

4
Tetrahedron
126.42, 126.32, 115.34. HRMS (ESI) m/z calcd for C18H14Cl+
CDCl3) δ 147.94, 143.85, 137.22, 133.42, 133.36, 131.84, 128.54,
ACCEPTED MANUSCRIPT
(M+H)+ 265.0778, found 265.0784.
128.48, 128.39, 127.84, 127.55, 126.74, 125.77, 124.81, 122.10,
+
121.75, 117.77. HRMS (ESI) m/z calcd for calcd for C20H12F6
(M)+ 366.0838, found 366.0841.
4.4. 2-(1-(4-bromophenyl)vinyl)naphthalene [2d]
1
Colorless oil, H NMR (400 MHz, CDCl3) δ 7.85 – 7.77 (m,
4.11. 2-(1-(2-fluorophenyl)vinyl)-6-methoxynaphthalene [2r]
3H), 7.74 (s, 1H), 7.51 – 7.42 (m, 5H), 7.27 – 7.23 (m, 3H), 5.60
(d, J = 0.8 Hz, 1H), 5.53 (d, J = 0.8 Hz, 1H). 13C NMR (101 MHz,
CDCl3) δ 149.15, 140.59, 138.44, 133.38, 133.15, 131.53, 130.15,
128.31, 128.00, 127.75, 127.44, 126.43, 126.33, 126.30, 122.02,
115.38. HRMS (ESI) m/z calcd for C18H14Br+ (M+H)+ 309.0273,
found 309.0273.
1
Colorless oil, H NMR (400 MHz, CDCl3) δ 7.68 (d, J = 8.6
Hz, 1H), 7.65 (d, J = 9.8 Hz, 1H), 7.60 (d, J = 1.8 Hz, 1H), 7.49
(dd, J = 8.6, 1.9 Hz, 1H), 7.39 – 7.27 (m, 2H), 7.21 – 7.14 (m,
1H), 7.13 – 7.04 (m, 3H), 5.85 (d, J = 1.2 Hz, 1H), 5.46 (s, 1H),
3.91 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 160.35 (d, J = 248.3
Hz), 158.00 , 144.21 , 135.88 , 134.31 , 131.77 (d, J = 3.6 Hz),
129.91 , 129.59 (d, J = 14.5 Hz), 129.51 (d, J = 8.1 Hz), 128.86 ,
126.87 , 125.97 , 125.44 , 124.12 (d, J = 3.7 Hz), 119.09 , 116.81
(d, J = 2.1 Hz), 115.96 (d, J = 22.3 Hz), 105.79 , 55.46 . HRMS
(ESI) m/z calcd for C19H16FO+ (M+H)+ 279.1179, found
279.1188.
4.5. 4-(1-(naphthalen-2-yl)vinyl)phenol [2e]
1
Colorless oil, H NMR (400 MHz, CDCl3) δ 7.86 – 7.76 (m,
4H), 7.51 – 7.43 (m, 3H), 7.40-7.34 (m, 5H), 5.59 (d, J = 1.2 Hz,
1H), 5.54 (d, J = 1.2 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ
150.18, 141.64, 139.02, 133.42, 133.10, 128.52, 128.37, 128.32,
127.94, 127.82, 127.73, 127.42, 126.54, 126.29, 126.15, 114.98.
HRMS (ESI) m/z calcd for C18H15O+ (M+H)+ 247.1117, found
247.1115.
4.12. 1-(1-(4-chlorophenyl)vinyl)naphthalene [3c]
1
Colorless oil, H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 8.4
Hz, 2H), 7.69 (d, J = 8.4 Hz, 1H), 7.51 – 7.39 (m, 3H), 7.35 –
7.29 (m, 1H), 7.22 – 7.21 (m, 4H), 5.95 (d, J = 1.2 Hz, 1H), 5.39
(d, J = 1.2 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 147.37,
139.65, 139.35, 133.84, 133.69, 131.80, 128.69, 128.40, 128.33,
128.05, 127.40, 126.35, 126.14, 125.92, 125.58, 116.80. HRMS
(ESI) m/z calcd for C18H14Cl+ (M+H)+ 265.0778, found 265.0779.
4.6. 2-(1-(3-chlorophenyl)vinyl)naphthalene [2g]
1
Colorless oil, H NMR (400 MHz, CDCl3) δ 7.84 – 7.73 (m,
4H), 7.50 – 7.35 (m, 4H), 7.33 – 7.19 (m, 3H), 5.60 (d, J = 0.8
Hz, 1H), 5.53 (d, J = 0.8 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ
149.02, 143.54, 134.35, 133.39, 133.16, 129.61, 128.55, 128.34,
128.03, 128.00, 127.75, 127.44, 126.70, 126.42, 126.34, 126.27,
115.91. HRMS (ESI) m/z calcd for C18H14Cl+ (M+H)+ 265.0779,
found 265.0780.
4.13. 1-(1-(3-methoxyphenyl)vinyl)naphthalene [3e]
1
Colorless oil, H NMR (400 MHz, CDCl3) δ 7.86 – 7.81 (m,
2H), 7.77 (d, J = 8.4 Hz, 1H), 7.50 – 7.45 (m, 1H), 7.43 – 7.39
(m, 2H), 7.32 (t, J = 8.0 Hz, 1H), 7.16 (t, J = 8.4 Hz, 1H), 6.91 –
6.86 (m, 2H), 6.81 – 6.76 (m, 1H), 5.96 (d, J = 1.6 Hz, 1H), 5.38
(d, J = 1.6 Hz, 1H), 3.71 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
159.74, 148.32, 142.76, 139.80, 133.80, 132.00, 129.46, 128.28,
128.10, 127.33, 126.52, 126.00, 125.79, 125.51, 119.53, 116.65,
112.97, 112.71, 55.31. HRMS (ESI) m/z calcd for C19H17O+
(M+H)+ 261.1274, found 261.1263.
4.7. 2-(1-(3-bromophenyl)vinyl)naphthalene [2h]
1
Colorless oil, H NMR (400 MHz, CDCl3) δ 7.84 – 7.73 (m,
4H), 7.54 (t, J = 1.6 Hz, 1H), 7.50 – 7.41 (m, 4H), 7.31 – 7.26 (m,
1H), 7.21 (d, J = 8.0 Hz, 1H), 5.60 (d, J = 0.8 Hz, 1H), 5.53 (d, J
= 0.8 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 148.93, 143.83,
138.28, 133.38, 133.16, 131.42, 130.92, 129.90, 128.34, 128.04,
127.75, 127.44, 127.17, 126.43, 126.34, 126.24, 122.59, 115.97.
HRMS (ESI) m/z calcd for C18H14Br+ (M+H)+ 309.0273, found
309.0274.
4.14. 1-(1-(3-bromophenyl)vinyl)naphthalene [3g]
1
Colorless oil, H NMR (400 MHz, CDCl3) δ 7.86 (d, J = 8.4
4.8. 2-(1-(2-methoxyphenyl)vinyl)naphthalene [2i]
Hz, 2H), 7.71 (d, J = 8.4 Hz, 1H), 7.54 – 7.31 (m, 6H), 7.16 (dt, J
= 8.0, 1.6, 1.2 Hz, 1H), 7.09 (t, J = 8.0 Hz, 1H), 5.96 (d, J = 1.2
Hz, 1H), 5.42 (d, J = 1.2 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ
147.23, 143.44, 139.04, 133.86, 131.77, 130.80, 130.04, 129.52,
128.41, 127.46, 126.29, 126.20, 125.94, 125.62, 125.55, 122.83,
117.72. HRMS (ESI) m/z calcd for C18H14Br+ (M+H)+ 309.0273,
found 309.0275.
1
Colorless oil, H NMR (400 MHz, CDCl3) δ 7.80 – 7.71 (m,
3H), 7.63 (d, J = 1.6 Hz, 1H), 7.53 (dd, J = 6.8, 1.6 Hz, 1H), 7.43
– 7.39 (m, 2H), 7.38 – 7.33 (m, 1H), 7.30 (dd, J = 7.6, 1.6 Hz,
1H), 7.01 (td, J = 7.6, 1.2 Hz, 1H), 6.92 (d, J = 8.4 Hz, 1H), 5.85
(d, J = 1.2 Hz, 1H), 5.41 (d, J = 1.2 Hz, 1H), 3.59 (s, 3H). 13C
NMR (101 MHz, CDCl3) δ 157.29, 147.09, 138.62, 133.49,
132.98, 131.49, 129.23, 128.38, 127.67, 127.63, 126.02, 125.80,
125.49, 124.87, 120.78, 116.12, 111.38, 55.74. HRMS (ESI) m/z
calcd for C19H17O+ (M+H)+ 261.1274, found 261.1269.
4.15. 1-(1-(2-bromophenyl)vinyl)naphthalene [3i]
1
Colorless oil, H NMR (400 MHz, CDCl3) δ 7.88 – 7.80 (m,
6H), 7.73 (d, J = 1.2 Hz, 1H), 7.54 – 7.49 (m, 2H), 7.41 (dd, J =
8.8, 2.0 Hz, 1H), 5.77 (s, 1H), 5.64 (s, 1H). 13C NMR (101 MHz,
CDCl3) δ 147.94, 143.85, 137.22, 133.42, 133.36, 131.84, 128.54,
128.48, 128.39, 127.84, 127.55, 126.74, 125.77, 124.81, 122.10,
4.9. 2-(1-(3,5-bis(trifluoromethyl)phenyl)vinyl)naphthalene [2l]
1
White solide,, H NMR (400 MHz, CDCl3) δ 7.88 – 7.80 (m,
6H), 7.73 (d, J = 1.2 Hz, 1H), 7.54 – 7.49 (m, 2H), 7.41 (dd, J =
8.8, 2.0 Hz, 1H), 5.77 (s, 1H), 5.64 (s, 1H). 13C NMR (101 MHz,
CDCl3) δ 147.94, 143.85, 137.22, 133.42, 133.36, 131.84, 128.54,
128.48, 128.39, 127.84, 127.55, 126.74, 125.77, 124.81, 122.10,
+
121.75, 117.77. HRMS (ESI) m/z calcd for calcd for C20H12F6
(M)+366.0838, found 366.0841.
4.16. 3-(1-(naphthalen-1-yl)vinyl)pyridine [3j]
+
121.75, 117.77. HRMS (ESI) m/z calcd for calcd for C20H12F6
1
(M)+ 366.0838, found 366.0841.
Brown solide, H NMR (400 MHz, CDCl3) δ 8.68 (s, 1H),
8.49 (d, J = 4.0 Hz, 1H), 7.87 (dt, J = 8.0, 1.2, 0.8 Hz, 2H), 7.70
(d, J = 8.4 Hz, 1H), 7.53 – 7.42 (m, 4H), 7.35 (ddd, J = 8.4, 6.8,
1.2 Hz, 1H), 7.17 (d, J = 8.0 Hz, 1H), 6.04 (d, J = 1.2 Hz, 1H),
5.51 (d, J = 1.2 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 148.86,
147.91, 145.58, 138.55, 136.78, 134.04, 133.90, 131.60, 128.57,
128.50, 127.48, 126.30, 126.14, 126.00, 125.58, 123.34, 118.03.
4.10. 3-(1-(naphthalen-2-yl)vinyl)pyridine [2n]
Brown solide,, 1H NMR (400 MHz, CDCl3) δ 7.88 – 7.80 (m,
6H), 7.73 (d, J = 1.2 Hz, 1H), 7.54 – 7.49 (m, 2H), 7.41 (dd, J =
8.8, 2.0 Hz, 1H), 5.77 (s, 1H), 5.64 (s, 1H). 13C NMR (101 MHz,

5
HRMS (ESI) m/z calcd for C17H14N+ (M+H)+232.1121, found
232.1121.
References and notes
ACCEPTED MANUSCRIPT
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4.17. 3-(1-(naphthalen-1-yl)vinyl)thiophene [3k]
1
White solide, H NMR (400 MHz, CDCl3) δ 7.90 (t, J = 8.0
Hz, 3H), 7.56 – 7.47 (m, 3H), 7.41 (ddd, J = 8.4, 6.8, 1.6 Hz, 1H),
7.35 – 7.29 (m, 2H), 6.81 (dd, J = 2.8, 1.6 Hz, 1H), 5.99 (d, J =
1.2 Hz, 1H), 5.35 (d, J = 1.2 Hz, 1H). 13C NMR (101 MHz,
CDCl3) δ 148.37, 143.15, 139.92, 133.76, 131.89, 128.27, 128.04,
126.71, 126.46, 125.99, 125.85, 125.69, 125.53, 123.37, 116.98,
115.06. HRMS (ESI) m/z calcd for C16H13S+ (M+H)+ 237.0732,
found 237.0733.
4.18. 1-fluoro-4-(1-(p-tolyl)vinyl)naphthalene [3n]
1
White solide, H NMR (400 MHz, CDCl3) δ 8.12 (d, J = 8.4
Hz, 1H), 7.74 (d, J = 8.4 Hz, 1H), 7.47 (t, J = 7.2 Hz, 1H), 7.38 –
7.31 (m, 2H), 7.30 – 7.21 (m, 1H), 7.20 – 7.11 (m, 3H), 7.05 (d, J
= 8.0 Hz, 2H), 5.92 (d, J = 1.2 Hz, H), 5.30 (d, J = 1.2 Hz, 1H),
2.30 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 158.57, 147.60,
138.27, 137.79, 136.14, 133.29, 129.25, 128.55, 127.44, 126.89,
126.62, 126.09, 123.93, 120.78, 115.83, 109.03, 21.27. HRMS
(ESI) m/z calcd for C19H16F+ (M+H)+ 263.1231, found 263.1231.
4.19. 1-methyl-4-(1-(p-tolyl)vinyl)naphthalene [3o]
1
White solide, H NMR (400 MHz, CDCl3) δ 8.00 (d, J = 8.4
Hz, 1H), 7.79 (d, J = 8.4 Hz, 1H), 7.45 (t, J = 8.0 Hz, 1H), 7.34 –
7.30 (m, 4H), 7.22 – 7.18 (m, 2H), 7.04 (d, J = 8.0 Hz, 2H), 5.91
(d, J = 1.6 Hz, 1H), 5.30 (d, J = 1.6 Hz, 1H), 2.71 (s, 3H), 2.29 (s,
3H). 13C NMR (101 MHz, CDCl3) δ 148.38, 138.54, 138.50,
137.56, 134.18, 132.86, 132.08, 129.18, 128.47, 127.24, 126.99,
126.64, 126.33, 125.62, 124.39, 115.33, 21.27, 19.70. HRMS
(ESI) m/z calcd for C20H19+ (M+H)+ 259.1481, found 259.1482.
4.20. 1-(1-(4-fluorophenyl)vinyl)-4-methylnaphthalene [3p]
1
White solide, H NMR (400 MHz, CDCl3) δ 8.01 (d, J = 8.3
Hz, 1H), 7.73 (d, J = 8.4 Hz, 1H), 7.46 (ddd, J = 8.3, 6.7, 1.3 Hz,
1H), 7.38 – 7.19 (m, 5H), 6.91 (t, J = 8.7 Hz, 2H), 5.88 (d, J =
1.3 Hz, 1H), 5.34 (d, J = 1.3 Hz, 1H), 2.72 (s, 3H). 13C NMR
(101 MHz, CDCl3) δ 162.45 (d, J = 247.1 Hz), 147.51, 137.92 ,
137.42 (d, J = 3.3 Hz), 134.41 , 132.83 , 131.78 , 128.30 (d, J =
8.0 Hz), 126.96 , 126.25 , 125.63 , 124.40 , 115.87 (d, J = 1.7 Hz),
115.23 (d, J = 21.6 Hz), 19.60. HRMS (ESI) m/z calcd for
C19H16F+ (M+H)+ 263.12306, found 263.12305.
4.21. 1-methoxy-4-(1-(p-tolyl)vinyl)naphthalene [3q]
1
White solide, H NMR (400 MHz, CDCl3) δ 8.29 (d, J = 8.4
Hz, 1H), 7.69 (d, J = 8.4 Hz, 1H), 7.46 – 7.29 (m, 4H), 7.21 (d, J
= 8.0 Hz, 2H), 7.04 (d, J = 8.0 Hz, 1H), 6.80 (d, J =7.6 Hz, 1H),
5.88 (d, J = 1.6 Hz, 1H), 5.30 (d, J = 1.6 Hz, 1H), 4.00 (s, 3H),
2.30 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 155.29, 148.27,
138.76, 137.51, 132.89, 132.46, 129.15, 128.45, 127.28, 126.69,
126.45, 125.77, 125.09, 122.18, 115.26, 103.39, 55.64, 21.26.
HRMS (ESI) m/z calcd for C20H19O+ (M+H)+ 275.1430, found
275.1430.
Acknowledgments
We gratefully acknowledge financial support of this work by
the National Natural Science Foundation of China (No.
21563025, No. 21463022), Shihezi University Training
Programme for Distinguished Youth Scholars (No.
2014ZRKXJQ05), and Start-Up Foundation for Young Scientists
of Shihezi University (RCZX201408).

6
Tetrahedron
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