Indium-promoted allylation of alkynes with allylic alcohols: Highly regioselective synthesis of halogen-substituted 1,4-dienes

Article abstract of DOI:10.1080/00397911.2011.604896

Indium-promoted allylation of alkynes by direct use of allyl alcohols as the allylating agents has been developed under mild conditions, in which a wide range of allylic alcohols and alkynes (both aromatic and aliphatic alkynes) could be tolerated, and the corresponding halogen-substituted 1,4-dienes were obtained in moderate to excellent yields.

Full text of DOI:10.1080/00397911.2011.604896

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Indium-Promoted Allylation of
Alkynes with Allylic Alcohols: Highly
Regioselective Synthesis of Halogen-
Substituted 1,4-Dienes
Hui-Lan Yue a b , Lei Ma c & Jian-Xin Ji a
a Chengdu Institute of Biology, Chinese Academy of Sciences,
Chengdu, China
b Graduate University of the Chinese Academy of Sciences, Beijing,
China
c Center for Drug Evaluation, State Food and Drug Administration,
Beijing, China
Accepted author version posted online: 13 Feb 2012.Version of
record first published: 08 Nov 2012.
To cite this article: Hui-Lan Yue , Lei Ma & Jian-Xin Ji (2013): Indium-Promoted Allylation of Alkynes
with Allylic Alcohols: Highly Regioselective Synthesis of Halogen-Substituted 1,4-Dienes, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
43:4, 600-610
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Synthetic Communications1, 43: 600–610, 2013
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2011.604896
INDIUM-PROMOTED ALLYLATION OF ALKYNES
WITH ALLYLIC ALCOHOLS: HIGHLY REGIOSELECTIVE
SYNTHESIS OF HALOGEN-SUBSTITUTED 1,4-DIENES
Hui-Lan Yue,1,2 Lei Ma,3 and Jian-Xin Ji1
1Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu, China
2Graduate University of the Chinese Academy of Sciences, Beijing, China
3Center for Drug Evaluation, State Food and Drug Administration,
Beijing, China
GRAPHICAL ABSTRACT
Abstract Indium-promoted allylation of alkynes by direct use of allyl alcohols as the
allylating agents has been developed under mild conditions, in which a wide range of allylic
alcohols and alkynes (both aromatic and aliphatic alkynes) could be tolerated, and the cor-
responding halogen-substituted 1,4-dienes were obtained in moderate to excellent yields.
Keywords Alkynes; allyl alcohols; allylation; halogen-substituted 1,4-dienes; indium(III) salt
INTRODUCTION
Allylation of carbon–carbon triple bonds is an important and useful method
for the construction of 1,4-dienes, which widely exist in naturally occurring and bio-
logically active compounds.[1] In general, allylmetal compounds such as allyl-Zn,
allyl-In, allyl-Si, and allyl-Sn are employed as allylating agents for this transform-
ation.[2] Nevertheless, the lack of facile and general methods for the preparation
of these allylic organometallics has limited their extensive applications. Recently,
alternative approaches for allylation of alkynes with metal and allylic halides to pro-
duce 1,4-dienes have been developed.[3] From the synthetic standpoint, the direct
allylation of alkynes by using allylic alcohols instead of allylmetal reagents and
allylic halides is an ideal process to access 1,4-dienes because of its advantages in
terms of synthetic efficiency, atom economy, and environmental sustainability.
Received April 19, 2011.
Address correspondence to Lei Ma, Center for Drug Evaluation, State Food and Drug
Administration, Beijing 100038, China, or Jian-Xin Ji, Chengdu Institute of Biology, Chinese Academy
of Sciences, Chengdu 610041, China. E-mail: mal@cde.org.cn; jijx@cib.ac.cn
600

ALLYLATION OF ALKYNES WITH ALLYLIC ALCOHOLS
601
Despite the tremendous advantages of using allylic alcohols as substrates, to
date, the direct allylation of alkynes with allylic alcohols to form substituted
1,4-dienes has very rarely been investigated.[4–7] Huang et al. described a palladium-
catalyzed allylation of alkynes with allylic alcohols in the presence of a stoichio-
metric amount of a CuCl2=HOAc, leading to chloro-substituted 1,4-dienes.[4]
Micalizio and Cha reported a Ti(Oi-Pr)4- or ClTi(Oi-Pr)3-mediated allylation of
alkynes with allylic alcohols in the presence of an excess amount of C5H9MgCl to
give substituted 1,4-dienes at ꢀ78 ꢁC.[5,6] Biswas et al. reported a FeX3-promoted
coupling of (E)-1,3-diphenylprop-2-en-1-ol with phenylacetylene to form chloro=
bromo-substituted 1,4-diene in moderate yield.[7] Obviously, these results are not
satisfactory with regard to yield and=or reaction conditions. Therefore, the develop-
ment of a mild, simple, convenient, and efficient method for the allylation of alkynes
with allylic alcohols to construct substituted 1,4-dienes is still in high demand and is
a challenging goal.
Herein, we describe a simple and efficient indium(III) halide–promoted allyla-
tion of unactivated alkynes with allyl alcohols to afford the halogen-substituted
1,4-dienes in moderate to excellent yields, in which indium halides not only
accomplish the formation of chemical bonds but also serve as halide sources under
mild conditions without any additives.
RESULTS AND DISCUSSION
In an initial experiment, cyclohex-2-enol 1a (0.25 mmol) was added to a
mixture of phenylacetylene 2a (0.38 mmol) and BiBr3 (0.025 mmol) in 1,2-
dibromoethane (DBE) at room temperature under air, and a poor yield (<5%) of
bromo-substituted 1,4-diene 3a was obtained (Table 1, entry 1). The addition of
NaBr (0.25 mmol) or KBr (0.25 mmol) as sources of bromine ions did not improve
this reaction (Table 1, entries 2 and 3). To our delight, 52% yield of 3a was isolated
when the loading of BiBr3 was increased to 0.08 mmol (Table 1, entry 4). Subse-
quently, the reaction activity of other metal halides was further investigated in this
reaction system (Table 1, entries 5–13). None of the desired product was detected
in the presence of TiBr4, AlBr3, ZnBr2, CuBr2, and AgBr salts (Table 1, entries 5–9).
Among BiBr3, PbBr2, AuBr3, SnBr4, and InBr3, InBr3 was proved to be the best
choice (Table 1, entries 10–13). Further exploration using InBr3 as promoter sug-
gested that DBE was the optimal reaction medium. After an extensive screening
of the reaction parameters (Table 1, entries 14–17), the best yield of 3a (82%) was
obtained by employing InBr3 (0.125 mmol) at room temperature in DBE (entry
17). However, when InCl3 was used as promoter, the corresponding chloro-
substituted 1,4-diene 3f was generated in very poor yield (<10%) under the optimal
reaction conditions. Fortunately, good yield (80%) of 3f could be obtained when the
temperature was raised to 60 ꢁC (entry 18).
With the optimized conditions in hand, the scope and limitation of this reac-
tion were further investigated using various combinations of alkynes and allylic alco-
hols in the presence of InX3 (X ¼ Br or Cl). As shown in Table 2, a variety of Br- or
Cl-substituted 1,4-dienes were obtained in moderate to excellent yields. In general,
aryl alkynes with electron-rich groups gave better yields of the expected products
than those bearing electron-deficient groups (3a–3h). Heteroaromatic alkynes such

602
H.-L. YUE, L. MA, AND J.-X. JI
Table 1. Optimization of the reaction conditionsa
Entry
MXn (mmol)
BiBr3 (0.025)
Solvent
Yield (%)b
1
2
DBE
DBE
DBE
DBE
DBE
DBE
DBE
DBE
DBE
DBE
DBE
DBE
DBE
DCE
CHCl3
CH2Cl2
DBE
DBE
5<
5<
5<
52
—
—
—
—
—
5<
36
64
73
52
33
54
82
80c
BiBr3 (0.025), NaBr (0.25)
BiBr3 (0.025), KBr (0.25)
BiBr3 (0.08)
3
4
5
TiBr4 (0.06)
AlBr3 (0.08)
6
7
ZnBr2 (0.125)
CuBr2 (0.125)
AgBr (0.25)
8
9
10
11
12
13
14
15
16
17
18
PbBr2 (0.125)
AuBr3 (0.08)
SnBr4 (0.06)
InBr3 (0.08)
InBr3 (0.08)
InBr3 (0.08)
InBr3 (0.08)
InBr3 (0.125)
InCl3 (0.125)
aReaction conditions: cyclohex-2-enol 1a (0.25 mmol), phenylacetylene 2a (0.38 mmol),
MXn (0.06–0.25 mmol).
bIsolated yields based on alcohol 1a.
cThe reaction was carried out at 60 ꢁC.
as 3-ethynylthiophene could also be used in the reaction to give the desired product
in 67% yield (3i). Notably, aliphalic alkynes were tolerated in this process, leading to
the corresponding products 3j–3l in moderate yields. However, none of the desired
products were observed when internal alkynes such as 1,2-diphenylethyne,
1-phenyl-1-butyne, and 4-octyne were applied in this reaction. With respect to allylic
alcohols, in addition to cyclohex-2-enol 1a, a series of cyclic allylic alcohols including
cyclopen-2-enol and substituted cyclohex-2-enols were all suitable substrates and
generated the corresponding products in moderate to excellent yields (3m–3q). Acyc-
lic allylic alcohol such as (E)-1,3-diphenylprop-2-en-1-ol was also compatible with
this reaction, affording the desired product 3r in 61% yield. Nevertheless, none of
the desired products were detected when simple aliphatic allylic alcohols such as
but-3-en-2-ol and penta-1,4-dien-3-ol were used as the substrates.
Based on these above results and previous studies,[8] a plausible pathway of this
coupling reaction is proposed in Scheme 1. Initially, allylic alcohol 1 was activated
by InX3(X ¼ Br or Cl) to generate the cationic intermediate 4. Then, the intermole-
cular addition of 4 to terminal alkyne 2 activated by InX3 would give alkenyl

603

604

ALLYLATION OF ALKYNES WITH ALLYLIC ALCOHOLS
605
Scheme 1. Possible pathway.
cation 5. Finally, the halide ion of the indium complex reacted with alkenyl cation 5,
leading to the desired product 3.
CONCLUSIONS
In summary, we have developed an efficient In(III) halide–promoted allylation
of alkynes by direct use of allylic alcohols as allylating agents. This mild and simple
reaction system provides an attractive approach to a large number of halogen-
substituted 1,4-dienes derivatives in moderate to excellent yields. Further investiga-
tions of reaction scope, precise mechanism, and synthetic applications are ongoing.
EXPERIMENTAL
All commercially available reagent-grade chemicals were purchased from
Aldrich, Acros, and Alfa Aesar chemical companies. All reagents and solvents were
used as received without further purification unless otherwise stated. NMR spectra
were recorded in CDCl3 on a Bruker Avance 600 spectrometer with tetramethylsi-
1
lane (TMS) as internal standard (600 MHz H, 150 MHz 13C) at room temperature,
the chemical shifts (d) are expressed in parts per million (ppm), and J values are given
in hertz (Hz). The following abbreviations are used to indicate the multiplicity: s
(singlet), d (doublet), t (triplet), m (multiplet), and br (broad). Mass analyses and
higher-resoultion mass spectra (HRMS) were obtained on an Agilent 5973 N
MSD mass spectrometer and a Waters Micromass GCT Premier mass spectrometer
by the electron impact (EI) method, respectively. Column chromatography was
performed on silica gel (200–300 mesh).
General Procedure for Allylation of Alkynes with Allylic Alcohols
The allylic alcohols (0.25 mmol) were added to a stirred mixture of alkynes
(0.38 mmol) and InX3 (0.125 mmol) in BrCH2CH2Br. The mixture was stirred for
about 3–6 h at room temperature. Upon completion of the reaction, the mixture
was filtered through silica gel and washed with EtOAc (10 mL) to give a brown sol-
ution. After filtration, the solvent was removed by vacuum evaporation. The residue
was purified by silica-gel flash column chromatography using hexane=EtOAc as the

606
H.-L. YUE, L. MA, AND J.-X. JI
eluent. The desired product was isolated as colorless oil, which was suitable for
analytical purposes.
Spectral Data for All the Compounds
1
1-Bromo-2-(cyclohex-2-enyl)vinyl)benzene (Table 2, 3a). E=Z (5.5:1); H
NMR (CDCl3, 600 MHz, ppm): (E)3a: d ¼ 7.54–7.27 (m, 5H), 6.06 (d, J ¼ 10.8 Hz,
1H), 5.76–5.72 (m, 1H), 5.47–5.45 (m, 1H), 2.87–2.83 (m, 1H), 2.05–1.41 (m, 6H);
(Z)3a: d ¼ 7.54–7.27 (m, 5H), 6.08 (d, J ¼ 8.7 Hz, 1H), 5.80–5.79 (m, 1H),
5.62–5.60 (m, 1H), 3.40 (m, 1H), 2.05–1.41 (m, 6H); 13C NMR (CDCl3, 150 MHz,
ppm): d ¼ 140.0, 138.9, 138.1, 135.2, 128.8, 128.6, 128.5, 128.4, 128.3, 128.2, 127.6,
120.2, 39.2, 37.4, 29.0, 28.0, 24.8, 24.7, 20.9, 20.6; HRMS (EI): calcd. for
C14H15Br, 262.0357; found, 262.0360.
1-(1-Bromo-2-(cyclohex-2-enyl)vinyl)-4-fluorobenzene (Table 2, 3b).
1
E=Z (4.5:1); H NMR (CDCl3, 600 MHz, ppm): (E)3b: d ¼ 7.50–6.99 (m, 4H), 6.06
(d, J ¼ 10.6 Hz, 1H), 5.76–5.73 (m, 1H), 5.45–5.43 (m, 1H), 2.83–2.79 (m, 1H),
2.03–1.41 (m, 6H); (Z)3b: d ¼ 7.50–6.99 (m, 4H), 6.01 (d, J ¼ 8.8 Hz, 1H),
5.81–5.79 (m, 1H), 5.60–5.58 (m, 1H), 3.38–3.37 (m, 1H), 2.03–1.41 (m, 6H); 13C
NMR (CDCl3, 150 MHz, ppm): d ¼ 163.3, 161.6, 138.5, 136.2, 135.2, 134.9, 130.7,
130.67, 129.4, 129.3, 129.0, 128.8, 128.4, 128.2, 128.0, 127.6, 123.1, 118.9, 115.4,
115.2, 115.1, 115.0, 39.2, 37.4, 29.0, 28.0 24.8, 24.7, 20.8, 20.6; HRMS (EI): calcd.
for C14H14BrF, 280.0263; found, 280.0268.
1-(1-Bromo-2-(cyclohex-2-enyl)vinyl)-4-methylbenzene (Table 2, 3c).
1
E=Z (1.5:1); H NMR (CDCl3, 600 MHz, ppm): (E)3c: d ¼ 7.42–7.11 (m, 4H), 6.04
(d, J ¼ 10.8 Hz, 1H), 5.74–5.72 (m, 1H), 5.47–5.45 (m, 1H), 2.87–2.85 (m, 1H),
2.36 (s, 3H), 2.03–1.42 (m, 6H); (Z)3c: d ¼ 7.42–7.11 (m, 4H), 6.03 (d, J ¼ 8.3 Hz,
1H), 5.80–5.78 (m, 1H), 5.62–5.60 (m, 1H), 3.39–3.38 (m, 1H), 2.35 (s, 3H),
2.03–1.42 (m, 6H); 13C NMR (CDCl3, 150 MHz, ppm): d ¼ 138.4, 138.3, 137.8,
137.2, 136.0, 134.4, 128.9, 128.85, 128.7, 128.6, 128.5, 128.3, 128.2, 127.5, 124.5,
120.4, 39.2, 37.4, 29.0, 28.1, 24.8, 24.7, 21.3, 21.1, 20.9, 20.6; HRMS (EI): calcd.
for C15H17Br, 276.0514; found, 276.0518.
1-(1-Bromo-2-(cyclohex-2-enyl)vinyl)-3-methylbenzene (Table 2, 3d).
1
E=Z (2.8:1); H NMR (CDCl3, 600 MHz, ppm): (E)3d: d ¼ 7.33–7.09 (m, 4H), 6.04
(d, J ¼ 10.6 Hz, 1H), 5.75–5.73 (m, 1H), 5.48–5.46 (m, 1H), 2.86–2.84 (m, 1H),
2.36 (s, 3H), 2.03–1.41 (m, 6H); (Z)3d: d ¼ 7.33–7.09 (m, 4H), 6.05 (d, J ¼ 8.6 Hz,
1H), 5.80–5.78 (m, 1H), 5.62–5.60 (m, 1H), 3.39 (m, 1H), 2.36 (s, 3H), 2.03–1.41
(m, 6H); 13C NMR (CDCl3, 150 MHz, ppm): d ¼ 139.9, 138.8, 138.0, 137.9, 135.0,
129.4, 129.2, 129.1, 128.6, 128.5, 128.3, 128.2, 128.1, 125.8, 124.8, 120.4, 39.2,
37.4, 29.0, 28.0, 24.8, 24.7, 21.4, 21.3, 20.9, 20.6; HRMS (EI): calcd. for C15H17Br,
276.0514; found, 276.0516.
1-(1-Bromo-2-(cyclohex-2-enyl)vinyl)-3-chlorobenzene (Table 2, 3e).
1
E=Z (3:1); H NMR (CDCl3, 600 MHz, ppm): (E)3e: d ¼ 7.52–7.20 (m, 4H), 6.08
(d, J ¼ 11.0 Hz, 1H), 5.77–5.75 (m, 1H), 5.45–5.43 (m, 1H), 2.82 (m, 1H),
2.04–1.40 (m, 6H); (Z)3e: d ¼ 7.52–7.20 (m, 4H), 6.10 (d, J ¼ 10.6 Hz, 1H),
5.82–5.80 (m, 1H), 5.59–5.58 (m, 1H), 3.39 (m, 1H), 2.04–1.40 (m, 6H); 13C NMR

ALLYLATION OF ALKYNES WITH ALLYLIC ALCOHOLS
607
(CDCl3, 150 MHz, ppm): d ¼ 140.5, 139.1, 136.5, 134.1, 129.5, 129.4, 128.9, 128.88,
128.6, 128.56, 128.3, 128.0, 127.74, 127.70, 126.99, 125.8, 122.6, 118.1, 39.2, 37.4,
28.9, 27.9, 24.8, 24.7, 20.8, 20.5; HRMS (EI): calcd. for C14H14BrCl, 295.9967;
found, 295.9963.
1
(1-Chloro-2-(cyclohex-2-enyl)vinyl)benzene (Table 2, 3f). E=Z (4:1); H
NMR (CDCl3, 600 MHz, ppm): (E)3f: d ¼ 7.58–7.28 (m, 5H), 5.82 (d, J ¼ 11.0 Hz,
1H), 5.76–5.74 (m, 1H), 5.49–5.47 (m, 1H), 2.93–2.91(m, 1H), 2.04–1.41 (m, 6H);
(Z)3f: d ¼ 7.58–7.28 (m, 5H), 6.02 (d, J ¼ 8.8 Hz, 1H), 5.80–5.78 (m, 1H),
5.61–5.59 (m, 1H), 3.47 (m, 1H), 2.04–1.41 (m, 6H); 13C NMR (CDCl3, 150 MHz,
ppm): d ¼ 138.2, 137.4, 133.9, 132.0, 131.5, 130.4, 128.7, 128.66, 128.5, 128.4,
128.3, 128.2, 126.4, 36.4, 36.2, 29.3, 28.2, 24.8, 24.7, 20.9, 20.6; HRMS (EI): calcd.
for C14H15Cl, 218.0862; found, 218.0863.
1-(1-Chloro-2-(cyclohex-2-enyl)vinyl)-4-methylbenzene (Table 2, 3g).
1
E=Z (4.6:1); H NMR (CDCl3, 600 MHz, ppm): (E)3g: d ¼ 7.46–7.13 (m, 4H), 5.78
(d, J ¼ 11.0 Hz, 1H), 5.75–5.73 (m, 1H), 5.48–5.47 (m, 1H), 2.93–2.91 (m, 1H),
2.36 (S, 3H), 2.03–1.40 (m, 6H); (Z)3g: d ¼ 7.46–7.13 (m, 4H), 5.96 (d, J ¼ 9.2 Hz,
1H), 5.77 (m, 1H), 5.61–5.59 (m, 1H), 3.45 (m, 1H), 2.35 (S, 3H), 2.03–1.40 (m,
6H); 13C NMR (CDCl3, 150 MHz, ppm): d ¼ 138.5, 138.2, 135.5, 134.5, 133.5,
132.0, 130.6, 130.56, 128.9, 128.87, 128.6, 128.4, 128.1, 126.3, 36.2, 29.3, 28.3,
24.9, 24.7, 21.3, 21.1, 20.9, 20.7; HRMS (EI): calcd. for C15H17Cl, 232.1019; found,
232.1020.
1-(1-Chloro-2-(cyclohex-2-enyl)vinyl)-3-methylbenzene (Table 2, 3h).
1
E=Z (3.2:1); H NMR (CDCl3, 600 MHz, ppm): (E)3h: d ¼ 7.38–7.10 (m, 4H), 5.80
(d, J ¼ 10.6 Hz, 1H), 5.76–5.74 (m, 1H), 5.49–5.47 (m, 1H), 2.93–2.90 (m, 1H),
2.38 (s, 3H), 2.04–1.41 (m, 6H); (Z)3h: d ¼ 7.38–7.10 (m, 4H), 5.99 (d, J ¼ 8.8 Hz,
1H), 5.78 (m, 1H), 5.61–5.59 (m, 1H), 3.46 (m, 1H), 2.36 (s, 3H), 2.04–1.41 (m,
6H); 13C NMR (CDCl3, 150 MHz, ppm): d ¼ 138.3, 138.0, 137.9, 137.3, 133.7,
131.3, 130.6, 129.3, 129.26, 129.1, 128.8, 128.5, 128.4, 128.1, 127.1, 125.7, 123.6,
36.3, 36.2, 29.2, 28.2, 24.8, 24.7, 21.4, 20.9, 20.6; HRMS (EI): calcd. for C15H17Cl,
232.1019; found, 232.1021.
3-(1-Bromo-2-(cyclohex-2-enyl)vinyl)thiophene (Table 2, 3i). E=Z
1
(1:1.4), H NMR (CDCl3, 600 MHz, ppm): (E)3i: d ¼ 7.43–7.14 (m, 3H), 6.04 (d,
J ¼ 10.6 Hz, 1H), 5.80–5,76 (m, 1H), 5.49–5.47 (m, 1H), 3.04 (m, 1H), 2.03–1.43
(m, 6H); (Z)3i: d ¼ 7.43–7.14 (m, 3H), 6.14 (d, J ¼ 8.8 Hz, 1H), 5.80–5,76 (m, 1H),
5.59–5.58 (m, 1H), 3.38 (m, 1H), 2.03–1.43 (m, 6H); 13C NMR (CDCl3, 150 MHz,
ppm): d ¼ 141.1, 138.8, 138.6, 133.7, 128.7, 128.4, 128.35, 128.3, 128.2, 125.9,
125.5, 125.3, 124.7, 123.9, 118.6, 114.5, 38.8, 37.5, 29.1, 28.1, 24.8, 24.7, 20.9, 20.6;
HRMS (EI): calcd. for C12H13BrS, 267.9921; found, 267.9910.
(Z)-3-(2-Bromo-3-cyclohexylprop-1-enyl)cyclohex-1-ene (Table 2, 3j).
The Z isomer of compound 3j could be isolated by silica-gel column chromato-
1
graphy): H NMR (CDCl3, 600 MHz, ppm): d ¼ 5.74–5.71 (m, 1H), 5.51–5.50 (m,
1H), 5.46 (d, J ¼ 8.8 Hz, 1H), 3.19 (m, 1H), 2.26 (d, J ¼ 7.0 Hz, 2H), 1.98 (m, 2H),
1.87–1.82 (m, 1H), 1.70–1.55 (m, 8H), 1.40–1.34 (m, 2H), 1.28–1.22 (m, 2H),
1.16–1.10 (m, 2H); 13C NMR (CDCl3, 150 MHz, ppm): d ¼ 133.4, 128.9, 127,7,

608
H.-L. YUE, L. MA, AND J.-X. JI
126.0, 49.2, 38.2, 35.6, 32.5, 28.3, 26.5, 26.2, 24.8, 20.9; HRMS (EI): calcd. for
C15H23Br, 282.0983; found, 282.0981.
3-(2-Bromooct-1-enyl)cyclohex-1-ene (Table 2, 3k). E=Z (1:1.6); 1H NMR
(CDCl3, 600 MHz, ppm): (E)3k: d ¼ 5.74 (d, J ¼ 10.3 Hz, 1H), 5.73–5.71 (m, 1H),
5.43–5.42 (m, 1H), 2.98 (m, 1H), 2.46–0.87 (m, 19H); (Z)3k: d ¼ 5.73–5.71 (m,
1H), 5.51–5.50 (m, 1H), 5.49 (d, J ¼ 8.4 Hz, 1H), 3.19 (m, 1H), 2.46–0.87 (m,
19H); 13C NMR (CDCl3, 150 MHz, ppm): d ¼ 136.1, 132.1, 128.9, 128.2, 127.7,
127.6, 126.1, 41.5, 38.1, 36.6, 35.7, 31.6, 31.5, 29.1, 28.3, 28.24, 28.21, 28.1, 28.0,
24.8, 24.7, 22.6, 20.9, 20.8, 14.0; HRMS (EI): calcd. for C14H23Br, 270.0983; found,
270.0989.
1
3-(2-Bromodec-1-enyl)cyclohex-1-ene (Table 2, 3l). E=Z (1:1); H NMR
(CDCl3, 600 MHz, ppm): (E)3l: d ¼ 5.73 (d, J ¼ 9.9 Hz, 1H), 5.73–5.72 (m, 1H),
5.43–5.42 (m, 1H), 2.97 (m, 1H), 2.45–0.87 (m, 23H); (Z)3l: d ¼ 5.73–5.72 (m, 1H),
5.51–5.50 (m, 1H), 5.49 (d, J ¼ 8.8 Hz, 1H), 3.19 (m, 1H), 2.45–0.87 (m, 23H); 13C
NMR (CDCl3, 150 MHz, ppm): d ¼ 136.0, 132.1, 128.9, 128.2, 127.7, 127.6, 126.1,
41.5, 38.2, 36.5, 35.7, 31.9, 29.4, 29.3, 29.2, 29.1, 28.6, 28.3, 28.27, 28.21, 28.1,
24.8, 24.7, 22.6, 20.9, 20.8, 14.1; HRMS (EI): calcd. for C16H27Br, 298.1296; found,
298.1296.
(1-Bromo-2-(4,4-dimethylcyclohex-2-enyl)vinyl)benzene (Table 2, 3m).
E=Z (4.3:1); 1H NMR (CDCl3, 600 MHz, ppm): (E)3m: d ¼ 7.53–7.27 (m, 5H),
6.04 (d, J ¼ 10.7 Hz, 1H), 5.48–5.46 (m, 1H), 5.33–5.31 (m, 1H), 2.80–2.79 (m,
1H), 1.70–0.78 (m, 10H); (Z)3m: d ¼ 7.53–7.27 (m, 5H), 6.05 (d, J ¼ 8.8 Hz, 1H),
5.51 (m, 1H), 5.40 (m, 1H), 3.34 (m, 1H), 1.70–0.78 (m, 10H); 13C NMR (CDCl3,
150 MHz, ppm): d ¼ 140.0, 139.0, 138.8, 137.9, 135.4, 135.1, 128.9, 128.85, 128.4,
128.3, 128.2, 127.6, 127.2, 125.9, 125.6, 124.6, 120.3, 39.4, 37.5, 35.6, 35.3, 31.4,
31.3, 30.1, 29.3, 29.1, 28.1, 26.1, 25.2; HRMS (EI): calcd. for C16H19Br, 290.0670;
found, 290.0664.
(1-Chloro-2-(4,4-dimethylcyclohex-2-enyl)vinyl)benzene (Table 2, 3n).
1
E=Z (8.3:1); H NMR (CDCl3, 600 MHz, ppm): (E)3n: d ¼ 7.58–7.29 (m, 5H), 5.80
(d, J ¼ 10.7 Hz, 1H), 5.49–5.47 (m, 1H), 5.35–5.32 (m, 1H), 2.86–2.82 (m, 1H),
1.74–0.78 (m, 10H); (Z)3n: d ¼ 7.58–7.29 (m, 5H), 5.81 (d, J ¼ 8.9 Hz, 1H), 5.51
(m, 1H), 5.42 (m, 1H), 3.42 (m, 1H), 1.74–0.78 (m, 10H); 13C NMR (CDCl3,
150 MHz, ppm): d ¼ 139.0, 138.7, 137.7, 137.4, 133.8, 131.4, 131.2, 130.5, 128.8,
128.7, 128.5, 128.4, 128.3, 127.9, 127.1, 126.4, 126.1, 125.8, 36.5, 36.4, 35.7, 35.4,
32.1, 31.3, 30.1, 29.3, 29.1, 28.2, 26.4, 25.4; HRMS (EI): calcd. for C16H19Cl,
246.1175; found, 246.1177.
(1-Bromo-2-(cyclopent-2-enyl)vinyl)benzene (Table 2, 3o). E=Z (1:1.1);
1H NMR (CDCl3, 600 MHz, ppm): (E)3o: d ¼ 7.53–7.27 (m, 5H), 6.04 (d,
J ¼ 10.3 Hz, 1H), 5.80–5.79 (m, 1H), 5.55–5.54 (m, 1H), 3.37–3.35 (m, 1H),
2.45–1.63 (m, 4H); (Z)3o: d ¼ 7.53–7.27 (m, 5H), 6.08 (d, J ¼ 8.4 Hz, 1H),
5.87–5.86 (m, 1H), 5.70–5.68 (m, 1H), 3.89–3.88 (m, 1H), 2.45–1.63 (m, 4H); 13C
NMR (CDCl3, 150 MHz, ppm): d ¼ 139.9, 138.8, 137.9, 135.4, 132.5, 132.3, 132.2,
129.1, 128.4, 128.3, 128.2, 127.6, 124.1, 119.6, 48.8, 46.9, 32.3, 32.1, 30.7, 30.1;
HRMS (EI): calcd. for C13H13Br, 248.0201; found, 248.0205.

ALLYLATION OF ALKYNES WITH ALLYLIC ALCOHOLS
609
(S)-(1-Bromo-2-(2-methyl-4-(prop-1-en-2-yl)cyclohex-2-enyl)vinyl)benzene
(Table 2, 3p). E=Z (1.9:1); 1H NMR (CDCl3, 600 MHz, ppm): (E)3p: d ¼ 7.54–7.28
(m, 5H), 6.23 (d, J ¼ 11.3 Hz, 1H), 5.44 (m, 1H), 4.73–4.71 (m, 2H), 2.76-2.74 (m,
1H), 2.32–1.60 (m, 11H); (Z)3p: d ¼ 7.54–7.28 (m, 5H), 6.20 (d, J ¼ 9.5 Hz, 1H),
5.52 (m, 1H), 4.73–4.71 (m, 2H), 3.35 (m, 1H), 2.32–1.60 (m, 11H); 13C NMR
(CDCl3, 150 MHz, ppm): d ¼ 149.5, 149.4, 140.1, 139.0, 137.5, 137.4, 137.1, 134.8,
134.6, 134.0, 128.9, 128.8, 128.4, 128.2, 127.8, 127.6, 125.1, 122.8, 120.6, 108.9,
42.8, 40.8, 37.1, 36.4, 33.7, 33.1, 30.8, 22.2, 22.1, 20.8, 20.7; HRMS (EI): calcd.
for C18H21Br, 316.0827; found, 316.0823.
(S)-(1-Chloro-2-(2-methyl-4-(prop-1-en-2-yl)cyclohex-2-enyl)vinyl)benzene
(Table 2, 3q). E=Z (1.7:1); 1H NMR (CDCl3, 600 MHz, ppm): (E)3q: d ¼ 7.59–7.29
(m, 5H), 5.99 (d, J ¼ 11.0 Hz, 1H), 5.44 (m, 1H), 4.73–4.71 (m, 2H), 2.83–2.80 (m,
1H), 2.33–1.62 (m, 11H); (Z)3q: d ¼ 7.59–7.29 (m, 5H), 6.14 (d, J ¼ 9.5 Hz, 1H),
5.52 (m, 1H), 4.73–4.71 (m, 2H), 3.41 (m, 1H), 2.33–1.62 (m, 11H); 13C NMR
(CDCl3, 150 MHz, ppm): d ¼ 149.4, 138.3, 137.5, 134.8, 134.3, 133.3, 132.6, 131.1,
131.0, 128.7, 128.65, 128.5, 128.4, 128.3, 126.6, 122.4, 108.9, 108.8, 40.0, 39.7,
37.0, 36.4, 34.0, 33.1, 30.8, 22.2, 22.1, 20.8, 20.7; HRMS (EI): calcd. for C18H21Cl,
272.1332; found, 272.1336.
((1Z,4E)-1-Bromopenta-1,4-diene-1,3,5-triyl)tribenzene (Table 2, 3r).
E=Z (3:1); 1H NMR (CDCl3, 600 MHz, ppm): (E)3r: d ¼ 7.60–7.21 (m, 15H),
6.61–6.32 (m, 3H), 4.28 (dd, J ¼ 10.4 Hz, J ¼ 6.5 Hz, 1H); (Z)3r: d ¼ 7.60–7.21 (m,
15H), 6.61–6.32 (m, 3H), 4.91 (dd, J ¼ 9.3 Hz, J ¼ 6.5 Hz, 1H); 13C NMR (CDCl3,
150 MHz, ppm): d ¼ 142.0, 139.7, 138.4, 137.1, 137.0, 134.5, 132.1, 131.0, 130.9,
130.8, 130.0, 128.8, 128.79, 128.72, 128.6, 128.4, 128.3, 127.9, 127.8, 127.7, 127.6,
127.5, 126.9, 126.3, 126.1, 122.3, 51.4, 49.5; HRMS (EI): calcd. for C23H19Br,
374.0670; found, 374.0666.
ACKNOWLEDGMENT
We are grateful for the financial support from the National Science
Foundation of China (20802072).
REFERENCES
1. (a) Trost, B. M.; Probst, G. D.; Schoop, A. J. Am. Chem. Soc. 1998, 120, 9228–9236; (b)
Wilson, S. R.; Zucker, P. A. J. Org. Chem. 1988, 53, 4682–4693; (c) Moreau, B.; Wu, J.
Y.; Ritter, T. Org. Lett. 2009, 11, 337–339; (d) Morten, C. J.; Jamison, T. F. Tetrahedron
2009, 65, 6648–6655; (d) Matsubara, R.; Jamison, T. F. J. Am. Chem. Soc. 2010, 132, 6880–
6881.
2. (a) Negishi, E. I.; Miller, J. A. J. Am. Chem. Soc. 1983, 105, 6761–6763; (b) Yoshikawa, E.;
Gevorgyan, V.; Asao, N.; Yamamoto, Y. J. Am. Chem. Soc. 1997, 119, 6781–6786; (c)
Shirakawa, E.; Yoshida, H.; Nakao, Y.; Hiyama, T. J. Am. Chem. Soc. 1999, 121, 4290–
4291; (d) Shirakawa, E.; Yamasaki, K.; Yoshida, H.; Hiyama, T. J. Am. Chem. Soc.
1999, 121, 10221–10222; (e) Shirakawa, E.; Yoshida, H.; Nakao, Y.; Hiyama, T. Org. Lett.
2000, 2, 2209–2211; (f) Yamamoto, Y.; Saito, Y.; Maruyama, K. J. Org. Chem. 1983, 48,
5409–5411; (g) Araki, S.; Imai, A.; Shimizu, K.; Yamada, M.; Mori, A.; Butsugan, Y. J.

610
H.-L. YUE, L. MA, AND J.-X. JI
Org. Chem. 1995, 60, 1841–1847; (h) Fujiwara, N.; Yamamoto, Y. J. Org. Chem. 1997, 62,
2318–2319; (i) Miura, K.; Saito, H.; Nakagawa, T.; Hondo, T.; Tateiwa, J.; Sonoda, M.;
Hosomi, A. J. Org. Chem. 1998, 63, 5740–5741; (j) Klaps, E.; Schmid, W. J. Org. Chem.
1999, 64, 7537–7546; (k) Fujiwara, N.; Yamamoto, Y. J. Org. Chem. 1999, 64, 4095–
4101; (l) Miura, K.; Saito, H.; Itoh, D.; Matsuda, T.; Fujisawa, N.; Wang, D.; Hosomi,
A. J. Org. Chem. 2001, 66, 3348–3355; (m) Kim, S. H.; Lee, H. S.; Kim, K. H.; Kim, S.
H.; Kim, J. N. Tetrahedron 2010, 66, 7065–7076.
3. (a) Ranu, B. C.; Majee, A. Chem. Commun. 1997, 1225–1226; (b) Ranu, B. C. Eur. J. Org.
Chem. 2000, 2347–2356; (c) Yadav, J. S.; Reddy, B. V. S.; Reddy, P. M. K.; Gupta, M. K.
Tetrahedron. Lett. 2005, 46, 8411–8413; (d) Albert, B. J.; Sivaramakrishnan, A.; Naka, T.;
Czaicki, N. L.; Koide, K. J. Am. Chem. Soc. 2007, 129, 2648–2659; (e) Lee, P. H.; Heo, Y.;
Seomoon, D.; Kim, S.; Lee, K. Chem. Commun. 2005, 1874–1876.
4. Huang, J. M.; Zhou, L.; Jiang, H. F. Angew. Chem. Int. Ed. 2006, 45, 1945–1949.
5. Kolundzic, F.; Micalizio, G. C. J. Am. Chem. Soc. 2007, 129, 15112–15113.
6. Lysenko, I. L.; Kim, K.; Lee, H. G.; Cha, J. K. J. Am. Chem. Soc. 2008, 130, 15997–16002.
7. Biswas, S.; Maiti, S.; Jana, U. Eur. J. Org. Chem. 2009, 2354–2359.
8. (a) Jana, U.; Biswas, S.; Maiti, S. Eur. J. Org. Chem. 2008, 5798–5804; (b) Ren, K.; Wang,
M.; Wang, L. Eur. J. Org. Chem. 2010, 565–571; (c) Kabalka, G. W.; Yao, M.-L.; Borella,
S.; Wu, Z.-Z. Org. Lett. 2005, 7, 2865–2867; (d) Xiang, S.-K.; Zhang, L.-H.; Jiao, N. Chem.
Commun. 2009, 6487–6489; (e) Liu, Z.-Q.; Wang, J.; Han, J.; Zhao, Y.; Zhou, B.
Tetrahedron. Lett. 2009, 50, 1240–1242.