Fe powder catalyzed highly efficient synthesis of alkenyl halides via direct coupling of alcohols and alkynes with aqueous HX as exogenous halide sources

Article abstract of DOI:10.1016/j.tet.2015.04.065

A simple and efficient catalytic method for the synthesis of alkenyl halides via direct coupling of alcohols and alkynes using aqueous HX (X=Cl, Br) as halide sources has been developed under mild conditions in the presence of Fe powder (1 mol %). In comp

Full text of DOI:10.1016/j.tet.2015.04.065

Tetrahedron 71 (2015) 4304e4311
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Fe powder catalyzed highly efficient synthesis of alkenyl halides via
direct coupling of alcohols and alkynes with aqueous HX as
exogenous halide sources
,
,
Yong-Rong Yang a b, Qiang Zhang a, Feng-Tian Du a, Jian-Xin Ji a
*
a Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041, China
b University of Chinese Academy of Sciences, Beijing 100049, China
a r t i c l e i n f o
a b s t r a c t
Article history:
A simple and efficient catalytic method for the synthesis of alkenyl halides via direct coupling of alcohols
and alkynes using aqueous HX (X¼Cl, Br) as halide sources has been developed under mild conditions in
the presence of Fe powder (1 mol %). In comparison with the high loading of FeX3 in previously reported
protocols, the present approach provides a remarkable attractive methodology to a diverse range of
alkenyl halides due to the advantages of simple operation and low-level metal contamination.
Ó 2015 Elsevier Ltd. All rights reserved.
Received 15 February 2015
Received in revised form 17 April 2015
Accepted 20 April 2015
Available online 25 April 2015
Keywords:
Alkenyl halides
Alcohols
Alkynes
Hydrohalides
Iron powder
1. Introduction
a mild, convenient and efficient methodology to access alkenyl
halides.
Alkenyl halides are very important building blocks and exten-
sively applied for the construction of various natural products and
pharmaceuticals.1 Furthermore, they have attracted increasingly
synthetic pursuit of chemists owing to their wide applications in
transition metals catalyzed cross-coupling transformations such as
the Suzuki,2 Sonogashira3 and Negishi reactions.4 Generally, alkenyl
halides are prepared from ketones or aldehydes using halogenating
reagents, such as phosphorus penthalides,5 acetyl halides6 and
POX3.7 Alternative procedures have also been developed, including
the addition of hydrohalides or alkyl halides to alkynes prompted
by alumina8 or ZnCl2,9 coupling reactions of alkynes and aldehydes
mediated by Lewis acids such as iron(III) halides,10 boron triha-
lides,11 or gallium(III) halides,12 ring opening of bis-activated
cyclopropenes promoted by stoichiometric magnesium halides,13
and the direct reaction of alcohols and vinylboron dihalides in the
presence of n-BuLi.14 However, most of these methods suffer from
several drawbacks such as drastic reaction conditions, the need of
extra steps to prepare active starting materials, low yields, or the
use of stoichiometric amounts of expensive and/or toxic reagents.
Therefore, there is still a great demand for the development of
Recently, Liu et al.15 reported an FeCl3$6H2O (5 mol %) catalyzed
method for the formation of alkenyl halides via addition of benzyl
halides to aryl alkynes. Jana and Wang et al.16 developed a new
synthetic strategy for preparing alkenyl halides via FeX3 promoted
coupling reaction of alcohols and alkynes, in which FeX3
(ꢀ33.3 mol %, X¼Cl, Br) were used not only as promoters but also as
halide sources (Scheme 1). In 2012, Bao et al.17 reported FeX3
(1 equiv, X¼Cl, Br) mediated reaction for the construction of alkenyl
halides from diphenylmethanes and ethynylbenzenes in the pres-
ence of stoichiometric DDQ. Yeh et al.18 described an FeCl3
(1.2 equiv) promoted method for the synthesis of alkenyl chlorides
with azaspirocyclic ring skeleton via intramolecular reaction of
alcohols with alkynes. Our research group also developed an Fe
(1 equiv)/I2 (1 equiv)/NaI (2 equiv) mediated system to deliver
alkenyl iodide compounds through coupling of alcohols and al-
kynes.19 More recently, Jiang et al.20 reported a Pd(II)-catalyzed
haloallylation approach to prepare 1,4-dienes in ionic liquids.
Herein, we disclose a convenient and efficient method for the
synthesis of alkenyl halides via direct coupling of various alcohols
and alkynes using aqueous HX (X¼Cl, Br) as halide sources in the
presence of Fe powder (1 mol %) (Scheme 1). In comparison with
the high loading of FeX3 in previously reported protocols (Fig. 1, B),
* Corresponding author. Tel.: þ86 28 82855463; fax: þ86 28 82855223; e-mail
the present approach provides
a
remarkable attractive
address: jijx@cib.ac.cn (J.-X. Ji).
http://dx.doi.org/10.1016/j.tet.2015.04.065
0040-4020/Ó 2015 Elsevier Ltd. All rights reserved.

Y.-R. Yang et al. / Tetrahedron 71 (2015) 4304e4311
4305
Table 1
methodology towards various alkenyl halides due to the advan-
tages of simple operation and low-level metal contamination (Fig.1,
Screening of the reaction conditionsa
A).
Entry
Catalyst
Solvent
Halide sources (mmol)
Yieldb (%)
1
2
3
4
5
6
7
8
FeCl3
FeCl3
FeCl3
FeCl3
FeCl2
Fe(acac)2
Fe
None
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CH2Cl2
DCE
NaCl (2.4)
LiCl (2.4)
(C4H9)4NCl (2.4)
HCl (2.4)
HCl (2.4)
HCl (2.4)
HCl (2.4)
HCl (2.4)
HCl (2.0)
HCl (3.0)
HCl (2.4)
HCl (2.4)
HCl (2.4)
HCl (2.4)
HCl (2.4)
HCl (2.4)
HCl (2.4)
HCl (2.4)
HBr (2.4)
Trace
Trace
Trace
86
86
82
87
n.d.
80
Scheme 1. Approaches for the synthesis of alkenyl halides.
9
10
11
12
13
14
15
16
17
18
19
86
Tracec
71d
74
60
80
n.d.
n.d.
n.d.
84
DBE
DMSO
CH3CN
THF
Fe
CHCl3
a
Reaction conditions: diphenylmethanol 1a (2.0 mmol), phenylacetylene 2a
(2.4 mmol), catalyst (1 mol %), halide sources (saturated aqueous solution of NaCl,
saturated aqueous solution of LiCl, 36% aqueous HCl or 47% aqueous HBr was used),
solvent (1 mL), 55 ꢁC, overnight.
b
Isolated yields based on alcohol 1a.
c
Reaction performed at 25 ꢁC.
Fig. 1. Comparation experiments between the present reaction system (A) and pre-
vious reaction system (B). (A): Diphenylmethanol 1a (5.43 mmol), phenylacetylene 2a
(1.2 equiv), Fe powder (1 mol %), and 36% aqueous HCl (1.2 equiv), CHCl3 (3 mL). (B):
Diphenylmethanol 1a (5.43 mmol), phenylacetylene 2a (1.2 equiv), FeCl3 (0.4 equiv),
CH2Cl2 (3 mL).
d
Reaction performed at 40 ꢁC.
such as cyclohex-2-enol and (E)-1, 3-diphenylprop-2-en-1-ol were
tolerated in this transformation, providing 1-halide-1,4-diene de-
rivatives in moderate to good yields (Table 2, 3len). With respect to
alkynes, aromatic terminal alkynes containing either electron-rich
or electron-deficient groups were all suitable substrates for this
protocol, furnishing the corresponding alkenyl halides in excellent
yields (Table 2, 3oev). In addition, heteroarylalkyne such as 3-
ethynylthiophene could be used in our case to give the desired
product in moderate yield (Table 2, 3w). Internal aromatic alkynes
such as 1-phenyl-1-propyne and 1-phenyl-1-butyne also reacted
smoothly, affording the corresponding products in good yields
(Table 2, 3xez). When aliphatic alkynes such as 1-hexyne and 1-
octyne were used in the present reaction system, the correspond-
ing products were obtained in 26% and 24% yields, respectively
(Table 2, 3a0e3b0).
The feasibility of gram-scale reaction was investigated with the
reaction of dibenzosuberol, phenylacetylene, and aqueous HX
(X¼Cl, Br) in the presence of 1 mol % iron powder (99.998% and 97%
purity), which could give the corresponding products 3f and 3g in
high yields without any significant loss of its reaction efficiency
(Scheme 2, Eqs. 1 and 2). Thus, this protocol could be employed as
a practical method to construct alkenyl halides.
Further investigations have been conducted to gain insights into
the reaction mechanism (Scheme 3). It is well known that FeX2 was
produced when Fe reacted with HX (X¼Cl, Br). Nevertheless, the
control experiments indicated that neither FeX2 (50 mol %) nor HX
(1.2 equiv) could promote independently the coupling reaction of
alcohols and alkynes to deliver the desired products (Scheme 3,
Eqs. 1 and 2). Previous reports showed that FeX3 could promote the
coupling reaction of alcohols and alkynes,16 so it is supposed that
FeX3 might catalyze the present reaction because Fe(II) could be
easily oxidized to Fe(III) in the presence of HX (X¼Cl, Br) under air.21
Further study supported this assumption and the desired product
3a was obtained in high yield (86%) when the present reaction was
conducted with the combination of 1.2 equiv HCl and 1 mol % FeCl3
2. Results and discussion
In an initial experiment, considering the high loading of FeX3 in
the previously reported reaction system of alcohols and alkynes,
halide sources such as aqueous NaCl, aqueous LiCl and tetrabuty-
lammonium chloride were investigated to lower the FeX3 loading.
Only a trace amount of desired product 3a was detected when the
model reaction of diphenylmethanol 1a and phenylacetylene 2a
was catalyzed by FeCl3 (1 mol %) in the presence of above mentioned
halide sources (Table 1, entries 1e3). To our delight, when aqueous
HCl was used as a chloride source in this reaction, the desired
product 3a was obtained in 86% isolated yield (Table 1, entry 4).
Subsequently, the catalytic activity of other iron catalysts was in-
vestigated in the presence of aqueous HCl (Table 1, entries 5e7).
Notably, cheap and easily available iron powder gave the desired
product in good yield (87%) (Table 1, entry 7). No desired product
was observed in the absence of catalyst (Table 1, entry 8). After an
extensive screening of the reaction parameters such as solvent,
temperature and the amount of aqueous HCl (Table 1, entries 9e18),
the best yield (87%) was obtained byemploying 1 mol % ironpowder
and aqueous HCl (2.4 mmol) in CHCl3 at 55 ꢁC (Table 1, entry 7). In
addition, when aqueous HBr was used as a bromide source, the
corresponding alkenyl bromide 3b was also generated in 84% yield
under the optimal reaction conditions (Table 1, entry 19).
Having identified the catalytic system, the scope and generality
were investigated by using various combinations of alkynes and
alcohols in the presence of aqueous HX (X¼Cl, Br). As shown in
Table 2, a series of alkenyl halides were obtained in moderate to
good yields. In general, the E isomers were given as the main
products. Various secondary benzylic alcohols were compatible
with the reaction, and the corresponding coupling products were
obtained in high yields (Table 2, 3aek). Moreover, allylic alcohols

Table 2
Results for reactions of alcohols with alkynes in the presence of Fe (1 mol %)/HXa,b

Y.-R. Yang et al. / Tetrahedron 71 (2015) 4304e4311
4307
of HX under air.21 Subsequently, alcohol 1 was activated by FeX3
and attacked by another alcohol 1 to generate dimeric ether 4. Next,
FeX3 coordinated with 4 to provide complex 7, then alkylation of 2
with 7 would give vinyl cation 5 and release intermediate 6, the
latter could participate in the catalytic cycle again. Finally, the nu-
cleophilic attack of halide ion on 5 produced the desired product 3.
Moreover, the pathway for direct haloalkylation of alkynes with
alcohols and aqueous HX to form alkenyl halides 3 might also be
involved in this transformation.
Furthermore, as shown in Table 3, a series of alkenyl halides
could also be obtained in moderate to good yields when the re-
actions of various alcohols with alkynes were separately performed
in the presence of FeX2 (1 mol %)/HX and FeX3 (1 mol %)/HX (X¼Cl,
Br) system. The above results supported the proposed reaction
mechanism.
Scheme 2. Gram-scale reactions.
or 1 mol % FeCl2 (Scheme 3, Eq. 3). Moreover, dimeric ether 4a was
detected in the model reaction of 1a and 2a, and the isolated 4a
reacted with 2a leading to the target product 3a in 80% yield under
the standard conditions (Scheme 3, Eqs. 4 and 5). The above results
suggested that FeX3 should be performed as the actual catalyst and
dimeric ether might be a key intermediate in the present reaction
for the synthesis of alkenyl halides.
Table 3
Results for reactions of alcohols with alkynes in the presence of FeX2 (1 mol %)/HXa,c
or FeX3 (1 mol %)/HXb,c
Scheme 3. Control experiments.
Based on the experimental observations22 and previous stud-
ies,16,19,23,24 the possible reaction pathways were proposed as
shown in Scheme 4. Initially, Fe transformed to FeX3 in the presence
3. Conclusions
In summary, we have developed a convenient and efficient
catalytic method for the synthesis of alkenyl halides from various
alcohols and alkynes using aqueous HX (X¼Cl, Br) as halide sources
with low loading of Fe powder (1 mol %). The present protocol,
which utilizes simple and cheap iron powder and readily available
starting materials, provides an attractive approach to a diverse
range of alkenyl halides in good to excellent yields. Further studies
on the detailed reaction mechanism and the synthetic application
are ongoing.
Scheme 4. Possible reaction pathways.

4308
Y.-R. Yang et al. / Tetrahedron 71 (2015) 4304e4311
4. Experimental section
4.5. Characterization data for reactions of alcohols with al-
kynes in the presence of Fe (1 mol %)/HX
4.1. General information
4.5.1. (3-Chloroprop-2-ene-1,1,3-triyl)tribenzene
(3a). 1H NMR
All chemicals and solvents were purchased from Aldrich,
Acros and Alfa Aesar Chemical Company as reagent grade and
used without further purification unless otherwise stated. Iron
powder (99.998% purity) was purchased from Alfa Aesar Chem-
ical Company. Iron powder (97% purity) was purchased from
Sigma Aldrich Chemical Company. 1H NMR and 13C NMR spectra
were recorded in CDCl3 on a Bruker Avance 600 (600 MHz 1H,
150 MHz 13C) or 400 (400 MHz 1H, 100 MHz 13C) spectrometer
with TMS as internal standard at room temperature, and the
(600 MHz, CDCl3, ppm): (E)-3a:
d
¼7.69e7.18 (m, 15H, aromatic),
6.53 (d, J¼11.0 Hz, 1H, CH), 4.86 (d, J¼11.0 Hz, 1H, CH); (Z)-3a:
d
¼7.69e7.18 (m, 15H, aromatic), 6.68 (d, J¼9.4 Hz, 1H, CH), 5.50 (d,
J¼9.5 Hz, 1H, CH); 13C NMR (CDCl3, 150 MHz, ppm):
¼143.4, 143.1,
d
137.0, 131.6, 131.5, 129.7, 129.0, 128.8, 128.7, 128.5, 128.4, 128.2,
126.7, 50.9, 50.8; MS (EI): m/z¼304; HRMS (EI) calcd for C21H17Cl
304.1019; found 304.1018.
4.5.2. (3-Bromoprop-2-ene-1,1,3-triyl)tribenzene (3b). 1H NMR
chemical shifts (
d
) were expressed in parts per million (ppm) and
(600 MHz, CDCl3, ppm): (E)-3b:
d
¼7.63e7.15 (m, 15H, aromatic),
J values were given in hertz (Hz). Abbreviations for NMR data:
s¼singlet; d¼doublet; t¼triplet; dd¼doublet of doublets;
dt¼doublet of triplets; m¼multiplet. Mass analyses and HRMS
were obtained on an Agilent 5973N MSD mass spectrometer and
a Waters Micromass GCT Premier mass spectrometer by the EI
method, respectively. X-ray crystallographic analysis was per-
formed with Rigaku-RAXIS-RAPID single-crystal diffractometer.
Column chromatography was performed on silica gel (100e200
mesh).
6.73 (d, J¼10.9 Hz, 1H, CH), 4.76 (d, J¼10.9 Hz, 1H, CH); (Z)-3b:
d
¼7.63e7.15 (m, 15H, aromatic), 6.72 (d, J¼9.2 Hz, 1H, CH), 5.42 (d,
J¼9.4 Hz, 1H, CH); 13C NMR (CDCl3, 150 MHz, ppm):
¼143.0, 142.8,
d
138.4, 135.6, 133.3, 128.8, 128.7, 128.4, 128.3, 128.2, 127.8, 126.7,
121.3, 53.7, 51.7; MS (EI): m/z¼348; HRMS (EI) calcd for C21H17Br
348.0514; found 348.0516.
4.5.3. (1-Chloro-3-(p-tolyl)prop-1-ene-1,3-diyl)dibenzene (3c). 1H
NMR (600 MHz, CDCl3, ppm): (E)-3c:
d¼7.64e7.03 (m, 14H, aro-
matic), 6.46 (d, J¼11.0 Hz, 1H, CH), 4.77 (d, J¼11.0 Hz, 1H, CH), 2.35
(s, 3H); (Z)-3c:
d
¼7.64e7.03 (m, 14H, aromatic), 6.62 (d, J¼9.5 Hz,
4.2. General experimental procedure
1H, CH), 5.41 (d, J¼9.4 Hz, 1H, CH), 2.35 (s, 3H); 13C NMR (CDCl3,
150 MHz, ppm):
d¼143.6, 140.4, 137.0, 136.3, 131.6, 131.3, 129.4,
To a stirred mixture of alcohol (2.0 mmol), alkyne (2.4 mmol),
and Fe powder (1 mol %) in chloroform (1 mL) was added hydro-
halide (2.4 mmol). The reaction mixture was stirred vigorously at
55 ꢁC overnight. Upon completion of the reaction, the mixture was
extracted with dichloromethane, dried and concentrated in vacuo
to provide raw product. Then the residue was purified by silica-gel
(100e200 mesh) column chromatography using petroleum ether
as the eluent to obtain a mixture of E and Z isomers of desired
product.
129.3, 128.8, 128.7, 128.7, 128.6, 128.4, 128.3, 128.3, 128.2, 128.1,
128.0, 126.7, 126.6, 50.5, 50.4, 21.0; MS (EI): m/z¼318; HRMS (EI)
calcd for C22H19Cl 318.1175; found 318.1178.
4.5.4. (1-Chloro-3-(4-chlorophenyl)prop-1-ene-1,3-diyl)dibenzene
(3d). 1H NMR (600 MHz, CDCl3, ppm): (E)-3d:
d
¼7.63e7.05 (m,
14H, aromatic), 6.40 (d, J¼10.9 Hz, 1H, CH), 4.76 (d, J¼10.9 Hz, 1H,
CH); (Z)-3d:
d
¼7.63e7.05 (m, 14H, aromatic), 6.56 (d, J¼9.2 Hz, 1H,
CH), 5.40 (d, J¼9.4 Hz, 1H, CH); 13C NMR (CDCl3, 150 MHz, ppm):
d¼142.8, 141.9, 136.8, 132.5, 132.0, 130.9, 129.7, 129.5, 129.0, 128.8,
4.3. The procedure of gram-scale reaction for the synthesis of
3f
128.8, 128.6, 128.5, 128.4, 128.3, 128.1, 126.9, 126.7, 50.2, 50.1; MS
(EI): m/z¼338; HRMS (EI) calcd for C21H16Cl2 338.0629; found
338.0627.
To a stirred mixture of dibenzosuberol (1 g, 4.76 mmol) and
phenylacetylene (5.71 mmol, 1.2 equiv) and Fe powder (1 mol %) in
chloroform (3 mL) was added 36% aqueous HCl (5.71 mmol,
1.2 equiv). The reaction mixture was stirred vigorously at 55 ꢁC for
18 h. Upon completion of the reaction, the mixture was extracted
with dichloromethane, dried and concentrated in vacuo to provide
raw product. Then the residue was purified by silica-gel (100e200
mesh) column chromatography using petroleum ether as the elu-
ent to obtain a mixture of E and Z isomers of desired product 3f in
81% yield (iron powder, 99.998% purity) or 80% yield (iron powder,
97% purity) as a colourless oil.
4.5.5. (1-Bromo-3-(4-chlorophenyl)prop-1-ene-1,3-diyl)dibenzene
(3e). 1H NMR (600 MHz, CDCl3, ppm): (E)-3e:
d
¼7.58e7.04 (m, 14H,
aromatic), 6.63 (d, J¼10.8 Hz, 1H, CH), 4.69 (d, J¼10.8 Hz, 1H, CH);
(Z)-3e:
d
¼7.58e7.04 (m, 14H, aromatic), 6.63 (d, J¼9.2 Hz, 1H, CH),
5.34 (d, J¼9.3 Hz, 1H, CH); 13C NMR (CDCl3, 150 MHz, ppm):
d
¼142.5, 141.6, 138.2, 135.0, 132.7, 132.5, 129.7, 129.5, 128.9, 128.8,
128.8, 128.7, 128.5, 128.3, 128.3, 128.1, 127.8, 126.9, 121.8, 53.1, 51.1;
MS (EI): m/z¼382; HRMS (EI) calcd for C21H16BrCl 382.0124; found
382.0119.
4.5.6. 5-(2-Chloro-2-phenylvinyl)-10,11-dihydro-5H-dibenzo[a,d][7]
4.4. The procedure of gram-scale reaction for the synthesis of
3g
annulene (3f). 1H NMR (600 MHz, CDCl3, ppm): (E)-3f:
d
¼7.58e7.05
(m, 13H, aromatic), 6.87 (d, J¼10.6 Hz, 1H, CH), 4.99 (d, J¼10.6 Hz,
1H, CH), 3.31e3.25 (m, 2H, CH2), 3.12e3.06 (m, 2H, CH2); (Z)-3f:
To a stirred mixture of dibenzosuberol (1 g, 4.76 mmol) and
phenylacetylene (5.71 mmol, 1.2 equiv) and Fe powder (1 mol %) in
chloroform (3 mL) was added 47% aqueous HBr (5.71 mmol,
1.2 equiv). The reaction mixture was stirred vigorously at 55 ꢁC for
18 h. Upon completion of the reaction, the mixture was extracted
with dichloromethane, dried and concentrated in vacuo to provide
raw product. Then the residue was purified by silica-gel (100e200
mesh) column chromatography using petroleum ether as the elu-
ent to obtain a mixture of E and Z isomers of desired product 3g in
78% yield (iron powder, 99.998% purity) or 78% yield (iron powder,
97% purity) as a colourless oil.
d
¼7.58e7.05 (m, 13H, aromatic), 6.89 (d, J¼8.2 Hz, 1H, CH), 5.45 (d,
J¼9.0 Hz, 1H, CH), 3.46e3.40 (m, 2H, CH2), 3.12e3.06 (m, 2H, CH2);
13C NMR (CDCl3, 150 MHz, ppm):
d
¼140.4, 140.1, 139.3, 139.0, 138.1,
137.3, 131.2, 131.0, 130.4, 130.2, 129.7, 128.9, 128.8, 128.6, 128.5,
128.4, 128.3, 127.1, 127.0, 126.7, 126.3, 52.6, 49.8, 33.4, 33.0; MS (EI):
m/z¼330; HRMS (EI) calcd for C23H19Cl 330.1175; found 330.1176.
4.5.7. 5-(2-Bromo-2-phenylvinyl)-10,11-dihydro-5H-dibenzo[a,d][7]
annulene (3g). 1H NMR (600 MHz, CDCl3, ppm): (E)-3g:
d
¼7.53e6.95 (m, 14H), 4.88 (d, J¼10.4 Hz, 1H, CH), 3.34e3.28 (m,
2H, CH2), 3.09e3.02 (m, 2H, CH2); (Z)-3g:
d¼7.53e6.95 (m, 14H),

Y.-R. Yang et al. / Tetrahedron 71 (2015) 4304e4311
4309
5.42 (d, J¼9.1 Hz, 1H, CH), 3.44e3.38 (m, 2H, CH2), 3.13e3.07 (m,
2H, CH2); 13C NMR (CDCl3, 150 MHz, ppm):
139.1, 138.8, 135.4, 133.2, 130.4, 130.2, 128.9, 128.8, 128.6, 128.5,
128.2, 127.9, 127.1, 127.0, 126.3, 120.8, 55.1, 51.6, 33.4, 33.0; MS (EI):
m/z¼374; HRMS (EI) calcd for C23H19Br 374.0670; found 374.0669.
126.4, 48.5, 48.5; MS (EI): m/z¼330; HRMS (EI) calcd for C23H19Cl
d¼140.0, 139.8, 139.3,
330.1175; found 330.1171.
4.5.14. ((4E)-1-Bromopenta-1,4-diene-1,3,5-triyl)tribenzene (3n). 1H
NMR (600 MHz, CDCl3, ppm): (E)-3n:
d
¼7.61e7.21 (m, 15H, aro-
matic), 6.62e6.32 (m, 3H, 3CH), 4.28 (dd, J¼10.2, 6.7 Hz, 1H, CH);
4.5.8. (1-Chlorobut-1-ene-1,3-diyl)dibenzene
(600 MHz, CDCl3, ppm): (E)-3h:
¼7.60e7.19 (m, 10H, aromatic),
6.15 (d, J¼10.8 Hz, 1H, CH), 3.63e3.57 (m, 1H, CH), 1.38 (d, J¼7.0 Hz,
(3h). 1H
NMR
(Z)-3n:
d
¼7.61e7.21 (m, 15H, aromatic), 6.62e6.32 (m, 3H, 3CH),
d
4.92 (t, J¼7.8 Hz,1H, CH); 13C NMR (CDCl3, 150 MHz, ppm):
¼142.0,
d
142.0, 139.8,138.5,137.2, 137.0, 134.6, 132.2,131.0, 131.0, 130.9, 130.1,
128.8, 128.8, 128.7, 128.6, 128.6, 128.4, 128.3, 127.9, 127.8, 127.7,
127.6, 127.5, 126.9, 126.4, 126.1, 121.3, 51.4, 49.5; MS (EI): m/z¼374;
HRMS (EI) calcd for C23H19Br 374.0670; found 374.0667.
3H, CH3); (Z)-3h:
d
¼7.60e7.19 (m, 10H, aromatic), 6.27 (d, J¼9.2 Hz,
1H, CH), 4.23e4.17 (m, 1H, CH), 1.50 (d, J¼7.0 Hz, 3H, CH3); 13C NMR
(CDCl3, 150 MHz, ppm):
d
¼145.0, 137.3, 134.3, 132.4, 130.2, 128.7,
128.6, 128.4, 128.3, 128.3, 127.1, 126.8, 126.6, 126.4, 39.8, 39.7, 22.4,
20.8; MS (EI): m/z¼242; HRMS (EI) calcd for C16H15Cl 242.0862;
found 242.0866.
4.5.15. (3-Chloro-3-(p-tolyl)prop-2-ene-1,1-diyl)dibenzene (3o). 1H
NMR (600 MHz, CDCl3, ppm): (E)-3o:
d
¼7.54e7.14 (m, 14H, aro-
matic), 6.44 (d, J¼11.0 Hz,1H, CH), 4.81 (d, J¼11.0 Hz,1H, CH), 2.39 (s,
4.5.9. (1-Bromobut-1-ene-1,3-diyl)dibenzene
(600 MHz, CDCl3, ppm): (E)-3i:
¼7.55e7.16 (m, 10H, aromatic),
6.37 (d, J¼10.7 Hz, 1H, CH), 3.53 (m, 1H, CH), 1.36 (d, J¼7.0 Hz, 3H,
(3i). 1H
NMR
3H, CH3); (Z)-3o:
d
¼7.54e7.14 (m, 14H, aromatic), 6.58 (d, J¼9.5 Hz,
d
1H, CH), 5.43 (d, J¼9.4 Hz,1H, CH), 2.37 (s, 3H, CH3); 13C NMR (CDCl3,
150 MHz, ppm):
d
¼143.5,138.9,134.1,131.7,131.0,129.1,129.0,128.7,
CH3); (Z)-3i:
d
¼7.55e7.16 (m, 10H, aromatic), 6.32 (d, J¼9.1 Hz, 1H,
128.6, 128.6, 128.4, 128.2, 126.6, 50.8, 21.3; MS (EI): m/z¼318; HRMS
CH), 4.16e4.10 (m, 1H, CH), 1.49 (d, J¼7.0 Hz, 3H, CH3); 13C NMR
(EI) calcd for C22H19Cl 318.1175; found 318.1173.
(CDCl3, 150 MHz, ppm):
d
¼144.6, 138.8, 138.5, 136.1, 128.8, 128.7,
128.6, 128.6, 128.5, 128.3, 128.2, 127.7, 127.1, 126.8, 126.4, 119.8, 42.6,
40.8, 22.0, 20.6; MS (EI): m/z¼286; HRMS (EI) calcd for C16H15Br
286.0357; found 286.0356.
4.5.16. (3-Chloro-3-(m-tolyl)prop-2-ene-1,1-diyl)dibenzene (3p). 1H
NMR (600 MHz, CDCl3, ppm): (E)-3p:
matic), 6.50 (d, J¼11.0 Hz, 1H, CH), 4.84 (d, J¼11.0 Hz, 1H, CH), 2.38
d
¼7.48e7.17 (m, 14H, aro-
(s, 3H, CH3); (Z)-3p:
d
¼7.48e7.17 (m, 14H, aromatic), 6.64 (d,
4.5.10. 1-Chloro-4-(4-chloro-4-phenylbut-3-en-2-yl)benzene
J¼9.5 Hz, 1H, CH), 5.48 (d, J¼9.4 Hz, 1H, CH), 2.41 (s, 3H, CH3); 13C
(3j). 1H NMR (600 MHz, CDCl3, ppm): (E)-3j:
d
¼7.58e7.09 (m, 9H,
NMR (CDCl3, 150 MHz, ppm):
d¼143.5, 143.2, 138.2, 138.1, 138.0,
aromatic), 6.08 (d, J¼10.7 Hz, 1H, CH), 3.56 (m, 1H, CH), 1.35 (d,
136.9, 133.7, 131.8, 131.4, 129.8, 129.6, 129.5, 129.4, 128.8, 128.7,
128.4, 128.3, 128.3, 127.4, 126.7, 125.8, 124.0, 50.9, 50.8, 21.5, 21.4;
MS (EI): m/z¼318; HRMS (EI) calcd for C22H19Cl 318.1175; found
318.1178.
J¼7.0 Hz, 3H, CH3); (Z)-3j: ¼7.58e7.09 (m, 9H, aromatic), 6.19 (d,
d
J¼9.1 Hz, 1H, CH), 4.16 (m, 1H, CH), 1.46 (d, J¼7.0 Hz, 3H, CH3); 13
C
NMR (CDCl3, 150 MHz, ppm):
d
¼143.5, 143.3, 137.9, 137.2, 133.7,
132.1, 131.8, 130.7, 128.8, 128.7, 128.6, 128.4, 128.3, 128.1, 126.5, 39.2,
39.1, 22.3, 20.8; MS (EI): m/z¼276; HRMS (EI) calcd for C16H14Cl2
276.0473; found 276.0470.
4.5.17. (3-Chloro-3-(o-tolyl)prop-2-ene-1,1-diyl)dibenzene (3q). 1H
NMR (600 MHz, CDCl3, ppm): (E)-3q:
d
¼7.36e7.06 (m, 14H, aro-
matic), 6.52 (d, J¼10.9 Hz, 1H, CH), 4.47 (d, J¼10.9 Hz, 1H, CH), 2.26
4.5.11. 1-(4-Chloro-4-phenylbut-3-en-2-yl)-4-methylbenzene
(s, 3H, CH3); (Z)-3q:
d
¼7.36e7.06 (m, 14H, aromatic), 6.23 (d,
(3k). 1H NMR (600 MHz, CDCl3, ppm): (E)-3k:
d
¼7.59e7.08 (m, 9H,
J¼9.5 Hz, 1H, CH), 5.43 (d, J¼9.5 Hz, 1H, CH), 2.36 (s, 3H, CH3); 13C
aromatic), 6.13 (d, J¼10.8 Hz, 1H, CH), 3.57 (m, 1H, CH), 2.35 (s, 3H,
NMR (CDCl3, 150 MHz, ppm):
d¼143.3, 143.1, 136.9, 136.4, 132.5,
CH3), 1.36 (d, J¼6.9 Hz, 3H, CH3); (Z)-3k:
d
¼7.59e7.08 (m, 9H, ar-
132.4, 131.4, 130.5, 130.4, 129.5, 129.1, 129.1, 128.8, 128.7, 128.6,
128.3, 128.2, 126.6, 125.9, 125.8, 50.7, 50.5, 19.9, 19.4; MS (EI): m/
z¼318; HRMS (EI) calcd for C22H19Cl 318.1175; found 318.1179.
omatic), 6.25 (d, J¼9.1 Hz, 1H, CH), 4.19e4.13 (m, 1H, CH), 2.35 (s,
3H, CH3), 1.48 (d, J¼7.0 Hz, 3H, CH3); 13C NMR (CDCl3, 150 MHz,
ppm):
d
¼142.0, 137.4, 136.0, 134.5, 129.9, 129.4, 129.3, 128.7, 128.6,
128.3, 128.3, 126.9, 126.6, 126.5, 39.3, 39.3, 22.5, 21.0, 20.9; MS (EI):
4.5.18. (3-Bromo-3-(o-tolyl) prop-2-ene-1,1-diyl)dibenzene (3r). 1H
m/z¼256; HRMS (EI) calcd for C17H17Cl 256.1019; found 256.1023.
NMR (600 MHz, CDCl3, ppm): (E)-3r:
matic), 6.80 (d, J¼10.8 Hz, 1H, CH), 4.49 (d, J¼10.8 Hz, 1H, CH), 2.29
d
¼7.41e7.11 (m, 14H, aro-
4.5.12. (1-Chloro-2-(cyclohex-2-en-1-yl)vinyl)benzene (3l). 1H NMR
(s, 3H, CH3); (Z)-3r:
d
¼7.41e7.11 (m, 14H, aromatic), 6.40 (d,
(600 MHz, CDCl3, ppm): (E)-3l:
d
¼7.59e7.28 (m, 5H, aromatic), 5.83
J¼9.4 Hz, 1H, CH), 5.43 (d, J¼9.4 Hz, 1H, CH), 2.38 (s, 3H, CH3); 13C
(d, J¼10.9 Hz, 1H, CH), 5.76 (m, 1H, CH), 5.49 (d, J¼9.8 Hz, 1H, CH),
NMR (CDCl3, 150 MHz, ppm):
d¼143.0, 142.8, 142.7, 137.7, 136.6,
2.93 (m, 1H, CH), 2.05e1.94 (m, 2H, CH2), 1.78e1.72 (m, 2H, CH2),
136.4, 135.2, 130.5, 130.3, 129.4, 129.0, 128.9, 128.7, 128.6, 128.6,
128.3,128.1,126.6,126.6,125.9,125.7,120.9, 53.2, 51.7,19.8,19.4; MS
(EI): m/z¼362; HRMS (EI) calcd for C22H19Br 362.0670; found
362.0666.
1.51e1.42 (m, 2H, CH2); (Z)-3l:
d
¼7.59e7.28 (m, 5H, aromatic), 6.03
(d, J¼8.9 Hz, 1H, CH), 5.85e5.79 (m, 1H, CH), 5.62 (d, J¼10.1 Hz, 1H,
CH), 3.48 (m, 1H, CH), 2.05e1.94 (m, 2H, CH2), 1.78e1.72 (m, 2H,
CH2), 1.51e1.42 (m, 2H, CH2); 13C NMR (CDCl3, 150 MHz, ppm):
d
¼137.4, 133.9, 131.5, 130.4, 128.7, 128.7, 128.5, 128.4, 128.3, 128.2,
4.5.19. (3-Chloro-3-(4-fluorophenyl)prop-2-ene-1,1-diyl)dibenzene
126.4, 36.4, 36.3, 29.3, 28.2, 24.8, 24.7, 20.9, 20.7; MS (EI): m/z¼218;
(3s). 1H NMR (600 MHz, CDCl3, ppm): (E)-3s:
d
¼7.61e7.02 (m, 14H,
HRMS (EI) calcd for C14H15Cl 218.0862; found 218.0863.
aromatic), 6.47 (d, J¼10.9 Hz, 1H, CH), 4.74 (d, J¼10.9 Hz, 1H, CH);
(Z)-3s:
d
¼7.61e7.02 (m, 14H, aromatic), 6.55 (d, J¼9.5 Hz, 1H, CH),
4.5.13. ((4E)-1-chloropenta-1,4-diene-1,3,5-triyl)tribenzene
5.41 (d, J¼9.3 Hz, 1H, CH); 13C NMR (CDCl3, 150 MHz, ppm):
(3m). 1H NMR (600 MHz, CDCl3, ppm): (E)-3m:
d
¼7.66e7.21 (m,
15H, aromatic), 6.61e6.25 (m, 3H, 3CH), 4.36 (dd, J¼10.5, 6.4 Hz,1H,
CH); (Z)-3m:
¼7.66e7.21 (m, 15H, aromatic), 6.61e6.25 (m, 3H,
3CH), 5.00e4.97 (m, 1H, CH); 13C NMR (CDCl3, 150 MHz, ppm):
d
¼163.6, 162.0, 143.2, 132.9, 131.8, 130.6, 130.6, 130.5, 128.7, 128.7,
128.3, 128.1, 126.7, 126.7, 115.5, 115.4, 115.3, 115.2, 50.9, 50.8; MS
(EI): m/z¼322; HRMS (EI) calcd for C21H16ClF 322.0925; found
322.0924.
d
d
¼142.3, 142.3, 138.0, 137.2, 137.1, 137.0, 133.5, 131.6, 131.3, 131.0,
130.8, 130.4, 130.4, 128.9, 128.8, 128.8, 128.7, 128.7, 128.6, 128.6,
128.4, 128.4, 128.3, 127.9, 127.7, 127.6, 127.5, 126.9, 126.9, 126.7,
4.5.20. (3-Bromo-3-(4-fluorophenyl)prop-2-ene-1,1-diyl)dibenzene
(3t). 1H NMR (600 MHz, CDCl3, ppm): (E)-3t:
d
¼7.57e7.01 (m, 14H,

4310
Y.-R. Yang et al. / Tetrahedron 71 (2015) 4304e4311
aromatic), 6.70 (d, J¼10.9 Hz, 1H, CH), 4.68 (d, J¼10.9 Hz, 1H, CH);
0.95e0.88 (m, 3H, CH3); (Z)-3b0:
d
¼7.33e7.17 (m, 10H, aromatic),
(Z)-3t:
d
¼7.57e7.01 (m, 14H, aromatic), 6.63 (d, J¼9.4 Hz, 1H, CH),
6.11 (d, J¼10.1 Hz, 1H, CH), 4.88 (d, J¼10.1 Hz, 1H, CH), 2.46 (t,
5.35 (d, J¼9.3 Hz, 1H, CH); 13C NMR (CDCl3, 150 MHz, ppm):
J¼7.4 Hz, 2H, CH2), 1.63e1.54 (m, 2H, CH2), 1.38e1.30 (m, 2H, CH2),
d
¼163.5, 161.9, 142.9, 142.7, 136.0, 134.4, 133.4, 130.8, 130.7, 129.6,
0.95e0.88 (m, 3H, CH3); 13C NMR (CDCl3, 150 MHz, ppm):
d¼143.5,
129.6,128.8,128.7,128.3,128.1,126.8,124.9,120.1,115.5,115.4,115.3,
115.1, 53.7, 51.8; MS (EI): m/z¼366; HRMS (EI) calcd for C21H16BrF
366.0419; found 366.0420.
143.4, 135.8, 135.6, 130.0, 128.6, 128.5, 128.3, 128.2, 127.4, 126.6,
126.4, 50.0, 49.9, 39.3, 33.8, 29.6, 29.5, 22.0, 21.8, 13.9, 13.8; MS (EI):
m/z¼284; HRMS (EI) calcd for C19H21Cl 284.1332; found 284.1334.
4.5.21. (3-Chloro-3-(3-chlorophenyl)prop-2-ene-1,1-diyl)dibenzene
4.5.28. (3-Chloronon-2-ene-1,1-diyl)dibenzene
(600 MHz, CDCl3, ppm): (E)-3c0:
(3b0). 1H
¼7.33e7.17 (m, 10H, aromatic),
NMR
(3u). 1H NMR (600 MHz, CDCl3, ppm): (E)-3u:
d
¼7.62e7.13 (m, 14H,
d
aromatic), 6.51 (d, J¼11.0 Hz, 1H, CH), 4.76 (d, J¼11.0 Hz, 1H, CH);
5.97 (d, J¼9.4 Hz, 1H, CH), 5.24 (d, J¼9.4 Hz, 1H, CH), 2.40 (t,
J¼7.3 Hz, 2H, CH2), 1.62e1.54 (m, 2H, CH2), 1.32e1.25 (m, 6H, 3CH2),
(Z)-3u:
d
¼7.62e7.13 (m, 14H, aromatic), 6.65 (d, J¼9.5 Hz, 1H, CH),
5.42 (d, J¼9.5 Hz, 1H, CH); 13C NMR (CDCl3, 150 MHz, ppm):
0.90e0.85 (m, 3H, CH3); (Z)-3c0:
d
¼7.33e7.17 (m, 10H, aromatic),
d
¼143.0, 138.5, 134.4, 132.5, 129.9, 129.7, 129.1, 128.9, 128.8, 128.7,
6.11 (d, J¼10.1 Hz, 1H, CH), 4.88 (d, J¼10.2 Hz, 1H, CH), 2.46 (t,
128.3, 128.1, 126.8, 50.8; MS (EI): m/z¼338; HRMS (EI) calcd for
21H16Cl2 338.0629; found 338.0630.
J¼7.3 Hz, 2H, CH2), 1.62e1.54 (m, 2H, CH2), 1.32e1.25 (m, 6H, 3CH2),
C
0.90e0.85 (m, 3H, CH3); 13C NMR (CDCl3, 150 MHz, ppm):
d
¼143.5,
143.4, 135.8, 135.6, 130.0, 128.6, 128.5, 128.3, 128.2, 127.5, 126.6,
126.4, 50.0, 49.9, 39.6, 34.0, 31.6, 31.5, 28.5, 28.3, 27.4, 27.2, 22.6,
22.5, 14.0; MS (EI): m/z¼312; HRMS (EI) calcd for C21H25Cl
312.1645; found 312.1645.
4.5.22. (3-Bromo-3-(3-chlorophenyl)prop-2-ene-1,1-diyl)dibenzene
(3v). 1H NMR (600 MHz, CDCl3, ppm): (E)-3v:
¼7.58e7.12 (m, 14H,
aromatic), 6.74 (d, J¼10.9 Hz, 1H, CH), 4.69 (d, J¼10.9 Hz, 1H, CH);
d
(Z)-3v:
d
¼7.58e7.12 (m, 14H, aromatic), 6.73e6.70 (m, 1H, CH), 5.36
(d, J¼9.4 Hz, 1H, CH); 13C NMR (CDCl3, 150 MHz, ppm):
d¼142.7,
4.5.29. Oxybis(methanetriyl)tetrabenzene (4a). 1H NMR (CDCl3,
142.4, 140.0, 136.6, 134.5, 134.3, 129.6, 129.5, 129.0, 128.8, 128.7,
128.3, 128.1, 127.8, 127.0, 126.8, 126.0, 119.3, 53.7, 51.7; MS (EI): m/
z¼382; HRMS (EI) calcd for C21H16BrCl 382.0124; found 382.0121.
600 MHz, ppm):
d
¼7.38 (d, J¼7.3 Hz, 8H), 7.33 (t, J¼7.5 Hz, 8H), 7.26
(t, J¼7.3 Hz, 4H), 5.41 (s, 2H); 13C NMR (CDCl3, 150 MHz, ppm):
d¼142.2, 128.4, 127.4, 127.3, 80.0; HRMS (ESI) calcd for C26H22NaO
373.1563; found: 373.1554.
4.5.23. 3-(1-Chloro-3,3-diphenylprop-1-en-1-yl)thiophene (3w). 1H
NMR (600 MHz, CDCl3, ppm): (E)-3w:
d
¼7.52e7.16 (m, 13H, aro-
4.6. Characterization data for reactions of alcohols with al-
kynes in the presence of FeX2 (1 mol %)/HX
matic), 6.41 (d, J¼10.7 Hz, 1H, CH), 4.97 (d, J¼10.7 Hz, 1H, CH); (Z)-
3w:
d
¼7.52e7.16 (m, 13H, aromatic), 6.60 (d, J¼9.5 Hz, 1H, CH), 5.41
(d, J¼9.4 Hz, 1H, CH); 13C NMR (CDCl3, 150 MHz, ppm):
d¼143.4,
4.6.1. 5-(2-Chloro-2-phenylvinyl)-10,11-dihydro-5H-dibenzo[a,d][7]
137.2, 131.6, 128.8, 128.6, 128.4, 128.2, 128.0, 126.7, 126.7, 125.7,
125.3, 51.0, 50.4; MS (EI): m/z¼310; HRMS (EI) calcd for C19H15ClS
310.0583; found 310.0585.
annulene (3f). 1H NMR (400 MHz, CDCl3, ppm): (E)-3f:
d
¼7.66e7.15
(m,13H, aromatic), 6.97 (d, J¼10.7 Hz,1H, CH), 5.10 (d, J¼10.5 Hz,1H,
CH), 3.40e3.31 (m, 2H, CH2), 3.20e3.13 (m, 2H, CH2); (Z)-3f:
d
¼7.66e7.15 (m, 13H, aromatic), 6.97 (d, J¼10.6 Hz, 1H, CH), 5.54 (d,
J¼8.9 Hz, 1H, CH), 3.53e3.48 (m, 2H, CH2), 3.20e3.13 (m, 2H, CH2);
13C NMR (CDCl3, 100 MHz, ppm):
4.5.24. (3-chloro-2-methylprop-2-ene-1,1,3-triyl)tribenzene (3x). 1H
NMR (600 MHz, CDCl3, ppm): (E)-3x:
matic), 5.18 (s, 1H, CH), 1.93 (s, 3H, CH3); (Z)-3x:
15H, aromatic), 4.47 (s, 1H, CH), 1.94 (s, 3H, CH3); 13C NMR (CDCl3,
150 MHz, ppm):
d
¼7.51e7.08 (m, 15H, aro-
d
¼140.4, 140.1, 139.4, 139.1, 138.1,
d
¼7.51e7.08 (m,
137.3,131.2,131.1,130.5,130.5,130.4,129.8,129.0,128.9,128.7,128.6,
128.5, 128.3, 127.2, 127.1, 126.8, 126.4, 52.7, 49.8, 33.4, 33.0; MS (EI):
m/z¼330; HRMS (EI) calcd for C23H19Cl 330.1175; found 330.1173.
d
¼142.0, 139.2, 135.3, 135.0, 129.5, 129.3, 129.2,
129.1, 128.8, 128.5, 128.3, 127.2, 126.8, 126.7, 126.5, 124.7, 123.9,
119.5, 59.7, 54.0, 17.8, 13.4; MS (EI): m/z¼318; HRMS (EI) calcd for
4.6.2. 5-(2-Bromo-2-phenylvinyl)-10,11-dihydro-5H-dibenzo[a,d][7]
C
22H19Cl 318.1175; found 318.1171.
annulene (3g). 1H NMR (400 MHz, CDCl3, ppm): (E)-3g:
d
¼7.62e7.10 (m,14H), 4.99 (d, J¼10.4 Hz,1H, CH), 3.43e3.34 (m, 2H,
CH2), 3.18e3.09 (m, 2H, CH2); (Z)-3g:
¼7.62e7.10 (m, 14H), 5.52 (d,
J¼9.0 Hz, 1H, CH), 3.54e3.47 (m, 2H, CH2), 3.18e3.09 (m, 2H, CH2);
13C NMR (CDCl3, 100 MHz, ppm):
4.5.25. (3-Chloro-2-ethylprop-2-ene-1,1,3-triyl)tribenzene (3y). 1H
NMR (600 MHz, CDCl3, ppm): (E)-3y:
¼7.54e7.12 (m, 15H, aro-
matic), 5.20 (s, 1H, CH), 2.50 (q, J¼7.4 Hz, 2H, CH2), 0.58 (t, J¼7.3 Hz,
d
d
d¼140.0, 139.9, 139.9, 139.4, 139.2,
3H, CH3); (Z)-3y:
d
¼7.54e7.12 (m, 15H, aromatic), 4.66 (s, 1H, CH),
138.8, 135.4, 133.3, 130.5, 130.3, 129.0, 128.9, 128.9, 128.6, 128.3,
127.9, 127.2, 127.1, 126.4, 120.9, 55.2, 51.7, 33.5, 33.1; MS (EI): m/
z¼374; HRMS (EI) calcd for C23H19Br 374.0670; found 374.0671.
2.61e2.54, 2.14e2.07 (m, 2H, CH2), 1.08 (t, J¼7.5 Hz, 3H, CH3); 13C
NMR (CDCl3, 150 MHz, ppm):
d
¼142.1, 140.4, 139.3, 129.6, 129.3,
128.8, 128.4, 128.3, 126.5, 54.0, 25.4, 12.3; MS (EI): m/z¼332; HRMS
(EI) calcd for C23H21Cl 332.1332; found 332.1330.
4.6.3. 3-(1-Chloro-3,3-diphenylprop-1-en-1-yl)thiophene (3w). 1H
NMR (400 MHz, CDCl3, ppm): (E)-3w:
d
¼7.57e7.22 (m, 13H, aro-
4.5.26. (3-Bromo-2-ethylprop-2-ene-1,1,3-triyl)tribenzene (3z). 1H
matic), 6.47 (d, J¼10.6 Hz, 1H, CH), 5.04 (d, J¼10.7 Hz, 1H, CH); (Z)-
NMR (600 MHz, CDCl3, ppm): (E)-3z:
d
¼7.51e7.08 (m, 15H, aro-
3w:
d
¼7.57e7.22 (m, 13H, aromatic), 6.66 (d, J¼9.5 Hz, 1H, CH), 5.47
matic), 5.17 (s, 1H, CH), 2.48 (q, J¼7.3 Hz, 2H, CH2), 0.54 (t, J¼7.3 Hz,
(d, J¼9.5 Hz, 1H, CH); 13C NMR (CDCl3, 100 MHz, ppm):
¼143.5,
d
3H, CH3); (Z)-3z:
d
¼7.51e7.08 (m, 15H, aromatic), 4.63 (s, 1H, CH),
137.2, 131.6, 128.8, 128.7, 128.4, 128.3, 128.0, 126.8, 126.8, 125.8,
125.3, 51.1, 50.4; MS (EI): m/z¼310; HRMS (EI) calcd for C19H15ClS
310.0583; found 310.0584.
2.58e2.51, 2.15e2.11 (m, 2H, CH2), 1.05 (t, J¼7.5 Hz, 3H, CH3); 13C
NMR (CDCl3, 150 MHz, ppm):
129.2, 128.7, 128.4, 128.2, 128.1, 126.5, 121.1, 54.1, 27.9, 12.3; MS (EI):
d¼143.0, 141.9, 141.0, 129.4, 129.3,
m/z¼376; HRMS (EI) calcd for C23H21Br 376.0827; found 376.0829.
4.6.4. (3-chloro-2-methylprop-2-ene-1,1,3-triyl)tribenzene (3x). 1H
NMR (400 MHz, CDCl3, ppm): (E)-3x:
matic), 5.16 (s, 1H, CH), 1.90 (s, 3H, CH3); (Z)-3x:
15H, aromatic), 4.43 (s, 1H, CH), 1.90 (s, 3H, CH3); 13C NMR (CDCl3,
100 MHz, ppm):
¼142.1, 139.2, 135.3, 135.0, 129.6, 129.3, 129.2,
128.9, 128.6, 128.5, 128.4, 127.3, 126.9, 126.8, 126.6, 124.8, 124.0,
d¼7.46e7.04 (m, 15H, aro-
4.5.27. (3-Chlorohept-2-ene-1,1-diyl)dibenzene
(600 MHz, CDCl3, ppm): (E)-3b0:
5.98 (d, J¼9.4 Hz, 1H, CH), 5.24 (d, J¼9.4 Hz, 1H, CH), 2.41 (t,
J¼7.4 Hz, 2H, CH2), 1.63e1.54 (m, 2H, CH2), 1.38e1.30 (m, 2H, CH2),
(3a0). 1H
¼7.33e7.17 (m, 10H, aromatic),
NMR
d¼7.46e7.04 (m,
d
d

Y.-R. Yang et al. / Tetrahedron 71 (2015) 4304e4311
4311
119.5, 59.7, 54.1, 17.9, 13.6; MS (EI): m/z¼318; HRMS (EI) calcd for
22H19Cl 318.1175; found 318.1173.
References and notes
C
1. For some representative examples, see: (a) Nicolaou, K. C.; Bulger, P. G.; Sarlah,
D. Angew. Chem., Int. Ed. 2005, 44, 4442; (b) Evans, D. A.; Starr, J. T. J. Am. Chem.
Soc. 2003, 125, 13531; (c) Kende, A. S.; Kawamura, K.; Devita, R. J. J. Am. Chem.
Soc. 1990, 112, 4070; (d) Kadota, I.; Takamura, H.; Sato, K.; Ohno, A.; Matsuda, K.;
Satake, M.; Yamamoto, Y. J. Am. Chem. Soc. 2003, 125, 11893; (e) Martin, S. F.;
Humphrey, J. M.; Ali, A.; Hillier, M. C. J. Am. Chem. Soc. 1999, 121, 866; (f) Nic-
olaou, K. C.; Webber, S. E. J. Am. Chem. Soc. 1984, 106, 5734; (g) Tietze, L. F.;
4.7. Characterization data for reactions of alcohols with al-
kynes in the presence of FeX3 (1 mol %)/HX
4.7.1. (1-Chlorobut-1-ene-1,3-diyl)dibenzene
(400 MHz, CDCl3, ppm): (E)-3h:
¼7.67e7.25 (m, 10H, aromatic),
6.22 (d, J¼10.8 Hz, 1H, CH), 3.71e3.62 (m, 1H, CH), 1.44 (d, J¼7.0 Hz,
(3h). 1H
NMR
d
€
Nobel, T.; Spescha, M. J. Am. Chem. Soc. 1998, 120, 8971; (h) Trost, B. M.; Dumas,
J. J. Am. Chem. Soc. 1992, 114, 1924; (i) Trost, B. M.; Dumas, J.; Villa, M. J. Am.
Chem. Soc. 1992, 114, 9836; (j) Miersch, A.; Hilt, G. Chem.dEur. J. 2012, 18, 9798.
2. (a) Miyaura, N.; Yamada, K.; Suginome, H.; Suzuki, A. J. Am. Chem. Soc. 1985, 107,
972; (b) Miyaura, N.; Suginome, H.; Suzuki, A. Tetrahedron 1983, 39, 3271; (c)
Miyaura, N.; Satoh, M.; Suzuki, A. Tetrahedron Lett. 1986, 27, 3745; (d) Miyaura,
N.; Suginome, H.; Suzuki, A. Tetrahedron Lett. 1981, 22, 127; (e) Miyaura, N.;
Suginome, H.; Suzuki, A. Tetrahedron Lett. 1983, 24, 1527; (f) Miyaura, N.; Ya-
3H, CH3); (Z)-3h:
d
¼7.67e7.25 (m, 10H, aromatic), 6.33 (d, J¼9.2 Hz,
1H, CH), 4.31e4.22 (m, 1H, CH), 1.55 (d, J¼7.0 Hz, 3H, CH3); 13C NMR
(CDCl3, 100 MHz, ppm):
d
¼145.0, 137.3, 134.4, 132.5, 130.2, 128.8,
128.7, 128.7, 128.5, 128.4, 128.3, 127.1, 126.8, 126.6, 126.5, 39.8, 39.7,
22.5, 20.9; MS (EI): m/z¼242; HRMS (EI) calcd for C16H15Cl
242.0862; found 242.0864.
ꢀ
mada, K.; Suzuki, A. Tetrahedron Lett. 1979, 20, 3437; (g) Soderquist, J. A.; Leon-
ꢀ
Colon, G. Tetrahedron Lett. 1991, 32, 43.
3. (a) Huynh, C.; Linstrumelle, G. Tetrahedron 1988, 44, 6337; (b) Rossi, R.; Bellina,
F.; Bechini, C.; Mannina, L.; Vergamini, P. Tetrahedron 1998, 54, 135; (c) Rossi, R.;
Carpita, A.; Quirici, M. G.; Gaudenzi, M. L. Tetrahedron 1982, 38, 631; (d) Alami,
M.; Crousse, B.; Linstrumelle, G. Tetrahedron Lett. 1994, 35, 3543; (e) Alami, M.;
Linstrumelle, G. Tetrahedron Lett. 1991, 32, 6109; (f) Myers, A. G.; Alauddin, M.
M.; Fuhry, M. A. M.; Dragovich, P. S.; Finney, N. S.; Harrington, P. M. Tetrahedron
Lett. 1989, 30, 6997; (g) Ratovelomanana, V.; Linstrumelle, G. Tetrahedron Lett.
1981, 22, 315; (h) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975,
16, 4467.
4.7.2. (1-Bromobut-1-ene-1,3-diyl)dibenzene
(400 MHz, CDCl3, ppm): (E)-3i:
¼7.65e7.19 (m, 10H, aromatic),
6.39 (d, J¼10.7 Hz, 1H, CH), 3.60e3.52 (m, 1H, CH), 1.39 (d, J¼6.9 Hz,
(3i). 1H
NMR
d
3H, CH3); (Z)-3i:
d
¼7.65e7.19 (m, 10H, aromatic), 6.35 (d, J¼9.1 Hz,
1H, CH), 4.18e4.14 (m, 1H, CH), 1.52 (d, J¼7.0 Hz, 3H, CH3); 13C NMR
(CDCl3, 100 MHz, ppm):
d
¼144.6, 138.7, 138.6, 128.8, 128.7, 128.6,
4. (a) Bellina, F.; Carpita, A.; De Santis, M.; Rossi, R. Tetrahedron Lett. 1994, 35,
6913; (b) Mazal, C.; Vaultier, M. Tetrahedron Lett. 1994, 35, 3089; (c) Negishi, E.;
Matsushita, H.; Okukado, N. Tetrahedron Lett. 1981, 22, 2715.
128.4, 128.4, 128.3, 127.7, 127.1, 126.8, 126.8, 126.5, 119.8, 42.6, 40.8,
22.1; MS (EI): m/z¼286; HRMS (EI) calcd for C16H15Br 286.0357;
found 286.0359.
5. (a) Kagan, J.; Arora, S. K.; Bryzgis, M.; Dhawan, S. N.; Reid, K.; Singh, S. P.; Tow, L.
J. Org. Chem. 1983, 48, 703; (b) Fry, A. J.; Moore, R. H. J. Org. Chem. 1968, 33, 425.
6. (a) Kodomari, M.; Nagaoka, T.; Furusawa, Y. Tetrahedron Lett. 2001, 42, 3105; (b)
Moughamir, K.; Mezgueldi, B.; Atmani, A.; Mestdagh, H.; Rolando, C. Tetrahe-
dron Lett. 1998, 39, 59.
4.7.3. 3-(1-Chloro-3,3-diphenylprop-1-en-1-yl)thiophene (3w). 1H
NMR (400 MHz, CDCl3, ppm): (E)-3w:
d
¼7.57e7.22 (m, 13H, aro-
€
€ €
7. (a) Lilienkampf, A.; Johansson, M. P.; Wahala, K. Org. Lett. 2003, 5, 3387; (b) Al-
awar, R. S.; Joseph, S. P.; Comins, D. L. J. Org. Chem. 1993, 58, 7732.
8. Kropp, P. J.; Daus, K. A.; Crawford, S. D.; Tubergen, M. W.; Kepler, K. D.; Craig, S.
L.; Wilson, V. P. J. Am. Chem. Soc. 1990, 112, 7433.
matic), 6.47 (d, J¼10.6 Hz, 1H, CH), 5.03 (d, J¼10.6 Hz, 1H, CH); (Z)-
3w:
d
¼7.57e7.22 (m, 13H, aromatic), 6.66 (d, J¼9.5 Hz, 1H, CH), 5.47
(d, J¼9.5 Hz, 1H, CH); 13C NMR (CDCl3, 100 MHz, ppm):
¼143.5,
d
9. (a) Hanack, M.; Weber, E. Chem. Ber. 1983, 116, 777; (b) Mayer, H.; Gonzalez, J. L.;
137.2, 131.6, 128.8, 128.7, 128.4, 128.3, 128.0, 126.8, 126.8, 128.7,
€
Ludtke, K. Chem. Ber. 1994, 127, 525.
125.8, 125.3, 51.1, 50.4; MS (EI): m/z¼310; HRMS (EI) calcd for
ꢀ
10. Miranda, P. O.; Díaz, D. D.; Padron, J. I.; Ramírez, M. A.; Martín, V. S. J. Org. Chem.
2005, 70, 57.
C
19H15ClS 310.0583; found 310.0583.
11. (a) Kabalka, G. W.; Wu, Z. Z.; Ju, Y. H. Org. Lett. 2002, 4, 1491; (b) Kabalka, G. W.;
Yao, M. L.; Borella, S.; Wu, Z. Z.; Ju, Y. H.; Quick, T. J. Org. Chem. 2008, 73, 2668.
12. Yadav, J. S.; Reddy, B. V. S.; Eeshwaraiah, B.; Gupta, M. K.; Biswas, S. K. Tetra-
hedron Lett. 2005, 46, 1161.
4.7.4. (3-chloro-2-methylprop-2-ene-1,1,3-triyl)tribenzene (3x). 1H
NMR (400 MHz, CDCl3, ppm): (E)-3x:
¼7.46e7.04 (m, 15H, aro-
matic), 5.16 (s, 1H, CH), 1.90 (s, 3H, CH3); (Z)-3x:
¼7.46e7.04 (m,
15H, aromatic), 4.43 (s, 1H, CH), 1.90 (s, 3H, CH3); 13C NMR (CDCl3,
100 MHz, ppm):
d
13. Wang, Y.; Lam, H. W. J. Org. Chem. 2009, 74, 1353.
d
14. Kabalka, G. W.; Yao, M. L.; Borella, S.; Wu, Z. Z. Org. Lett. 2005, 7, 2865.
15. Liu, Z. Q.; Wang, J. G.; Zhao, Y. K.; Zhou, B. Adv. Synth. Catal. 2009, 351, 371.
16. (a) Biswas, S.; Maiti, S.; Jana, U. Eur. J. Org. Chem. 2009, 2354; (b) Ren, K.; Wang,
M.; Wang, L. Eur. J. Org. Chem. 2010, 565; (c) Liu, Z. Q.; Wang, J. G.; Han, J.; Zhao,
Y. K.; Zhou, B. Tetrahedron Lett. 2009, 50, 1240.
17. Yang, J.; Chen, D.; Bao, W. Tetrahedron Lett. 2012, 53, 3984.
18. (a) Yeh, M.-C. P.; Fang, C.-W.; Lin, H.-H. Org. Lett. 2012, 14, 1830; (b) Yeh, M. C. P.;
Liang, C. J.; Fan, C. W.; Chiu, W. H.; Lo, J. Y. J. Org. Chem. 2012, 77, 9707.
19. Li, M.-M.; Zhang, Q.; Yue, H.-L.; Ma, L.; Ji, J.-X. Tetrahedron Lett. 2012, 53, 317.
20. Li, J.; Yang, S.; Wu, W.; Qi, C.; Deng, Z.; Jiang, H. Tetrahedron 2014, 70, 1516.
21. (a) Posner, A. M. Trans. Faraday Soc. 1953, 49, 382; (b) Swaminathan, K.; Sub-
ramanian, C.; Sridhar Rao, C. Hydrometallurgy 1981, 6, 339; (c) Morgan, B.; La-
hav, O. Chemosphere 2007, 68, 2080; (d) Porsch, K.; Kappler, A. Environ. Chem.
2011, 8, 190.
d
¼142.1, 139.2, 135.0, 129.6, 129.5, 129.3, 129.2,
128.9, 128.6, 128.5, 128.5, 127.4, 127.0, 126.8, 126.7, 124.9, 124.0,
119.6, 59.7, 54.1, 18.0, 13.6; MS (EI): m/z¼318; HRMS (EI) calcd for
C
22H19Cl 318.1175; found 318.1174.
Acknowledgements
We thank the National Natural Science Foundation of China
(21172213) for financial support.
22. See Supplementary data for details.
23. Sanz, R.; Miguel, D.; Martínez, A.; Alvarez-Gutierrez, J. M.; Rodríguez, F. Org.
ꢀ
ꢀ
Supplementary data
Lett. 2007, 9, 2027.
24. Yao, M. L.; Quick, T. R.; Wu, Z. Z.; Quinn, M. P.; Kabalka, G. W. Org. Lett. 2009, 11,
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2015.04.065.
2647.