First synthesis of both 1-aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles and 1-aryl-4-[(Z)-1-(trimethylsilyl)alk-1-enyl]-1H-1,2,3-triazoles: assembly of π-extended 1,2,3-triazoles using a cross-coupling/click reaction sequence

Article abstract of DOI:10.1016/j.tet.2016.05.055

A practical and general synthetic approach to a series of π-extended 1,2,3-triazoles with both aryl and alkenyl moieties on the triazole ring is described. Synthesis of 1-aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles can be achieved by the click reaction between terminal conjugated (E)-enynes, prepared by copper-mediated cross-coupling reaction of (E)-alk-1-enyldisiamylboranes with (trimethylsilyl)ethynyl bromide, and aryl azides, prepared from arylboronic acids and sodium azide in another flask and employed for the following click reaction without any purification. 1-Aryl-4-[(Z)-1-(trimethylsilyl)alk-1-enyl]-1H-1,2,3-triazoles can be also synthesized by a sequential three-step reaction, which involves copper-mediated cross-coupling reaction of (Z)-1-(trimethylsilyl)alk-1-enyldicyclohexylboranes with (trimethylsilyl)ethynyl bromide to form (Z)-1,3-bis(trimethylsilyl)alk-3-en-1-ynes, deprotection of the trimethylsilyl group on the alkynyl carbon atom to generate (Z)-3-(trimethylsilyl)alk-3-en-1-ynes and click reaction with aryl azides prepared in the same manner as described above. Both synthetic routes are tolerant of a wide range of functional groups with moderate to good yields.

Full text of DOI:10.1016/j.tet.2016.05.055

Accepted Manuscript
First synthesis of both 1-aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles and 1-aryl-4-[(Z)-1-
(trimethylsilyl)alk-1-enyl]-1H-1,2,3-triazoles: assembly of π-extended 1,2,3-triazoles
using a cross-coupling/click reaction sequence
Asuka Oikawa, Gan Kindaichi, Yasutaka Shimotori, Masayuki Hoshi
PII:
S0040-4020(16)30462-8
10.1016/j.tet.2016.05.055
TET 27782
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 8 April 2016
Revised Date: 14 May 2016
Accepted Date: 20 May 2016
Please cite this article as: Oikawa A, Kindaichi G, Shimotori Y, Hoshi M, First synthesis of both 1-
aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles and 1-aryl-4-[(Z)-1-(trimethylsilyl)alk-1-enyl]-1H-1,2,3-triazoles:
assembly of π-extended 1,2,3-triazoles using a cross-coupling/click reaction sequence, Tetrahedron
(2016), doi: 10.1016/j.tet.2016.05.055.
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ACCEPTED MANUSCRIPT
1
) CuI
NaOH
Me SiC
R
1) Cu(acac)
1M NaOMe
Me SiC CBr
2
N
N
Ar
Ar
N
N
B
N
N
3
CBr
R
3
2
) ArN [+ Cu(OAc)
Na ascorbate
M NaOMe
3
2
]
R2
R1
2) ArN3 [+ Cu(OAc)2]
Na ascorbate
R1
R1
Me
3
Si
R2 = H or Me
3
Si
1

ACCEPTED MANUSCRIPT
First synthesis of both
1
-aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles and
1
-aryl-4-[(Z)-1-(trimethylsilyl)alk-1-enyl]-1H-1,2,3-triazoles:
Assembly of π-extended 1,2,3-triazoles using a
cross-coupling/click reaction sequence
Asuka Oikawa, Gan Kindaichi, Yasutaka Shimotori, Masayuki Hoshi*
Department of Biotechnology and Environmental Chemistry, Kitami Institute of
Technology, 165 Koen-cho, Kitami, Hokkaido 090-8507, Japan
Fax +81(157)247719; E-mail: hoshi-m@chem.kitami-it.ac.jp
Abstract: A practical and general synthetic approach to a series of π-extended
1
,2,3-triazoles with both aryl and alkenyl moieties on the triazole ring is described.
Synthesis of 1-aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles can be achieved by the click
reaction between terminal conjugated (E)-enynes, prepared by copper-mediated
cross-coupling reaction of (E)-alk-1-enyldisiamylboranes with (trimethylsilyl)ethynyl
bromide, and aryl azides, prepared from arylboronic acids and sodium azide in another
flask and employed for the following click reaction without any purification.
1
-Aryl-4-[(Z)-1-(trimethylsilyl)alk-1-enyl]-1H-1,2,3-triazoles can be also synthesized
by a sequential three-step reaction, which involves copper-mediated cross-coupling
reaction of (Z)-1-(trimethylsilyl)alk-1-enyldicyclohexylboranes with
trimethylsilyl)ethynyl bromide to form (Z)-1,3-bis(trimethylsilyl)alk-3-en-1-ynes,
deprotection of the trimethylsilyl group on the alkynyl carbon atom to generate
Z)-3-(trimethylsilyl)alk-3-en-1-ynes and click reaction with aryl azides prepared in the
(
(
same manner as described above. Both synthetic routes are tolerant of a wide range of
functional groups with moderate to good yields.
Key words: 1,2,3-triazole, cross-coupling, click reaction, deprotection, alkenylborane,
arylboronic acid, (trimethylsilyl)ethynyl bromide
1
. Introduction
1

ACCEPTED MANUSCRIPT
Since Sharpless and Meldal independently pioneered the copper(I)-catalyzed
,3-dipolar cycloaddition reaction between organic azides and terminal alkynes to give
1
1
1
,4-disubstituted 1,2,3-triazoles exclusively, a wide variety of strategies have been
2
developed for the cycloaddition reaction, the so-called click reaction. As well as
3
showing biological activities, compounds bearing 1,2,3-triazole moiety have found a
4
large number of applications in different fields such as bioconjugation and materials
5
science. The 1,2,3-triazole scaffold is stable not only under acidic and basic conditions
but also under oxidative and reductive conditions. The chemically robust properties can
be attributed to the heterocyclic aromatic system. Assembling further π-extended
1
,2,3-triazoles can be performed by introduction of substituents such as aryl and alkenyl
groups into 1-, 4-, and 5-positions of the triazole ring. The extension of conjugated
system on 1,2,3-triazole ring, in fact, has been realized in the click reaction by making a
choice from the substrates. Thus, use of arylethynes as terminal alkynes gives 4- or
2
,6
5
-aryl 1,2,3-triazoles upon choosing the reaction conditions and use of aryl and
7
-9
7a,h,8a,10
alkenyl azides furnishes 1-aryl and 1-alkenyl
1,2,3-triazoles, respectively.
Although there are several reports on the formation of 4- or 5-alkenyl
6
a,h,7a,c,11
1
,2,3-triazoles,
the precursor of the alkenyl group is limited to only a few
conjugated enynes such as 1-ethynylcyclohexene. The click reaction using terminal
12
conjugated (E)-enynes (2), to our knowledge, is the only our previous report, in which
the reaction with in situ generated various benzyl azides proceeded at room temperature
to afford a wide range of 1-arylmethyl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles in high
yields. As our continued interest in assembling π-extended compounds utilizing in situ
1
3
generated terminal conjugated enynes,
copper(I)-catalyzed click reaction with aryl azides to extend π-conjugation at the
-position as well as at the 4-position of 1,2,3-triazole. Herein, we report the first
we focused our attention on the
1
synthesis of both 1-aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles (3) through a sequential
two-step reaction and 1-aryl-4-[(Z)-1-(trimethylsilyl)alk-1-enyl]-1H-1,2,3-triazoles (6)
through a sequential three-step reaction. The present protocol provides a practical and
general way to access π-extended 1,2,3-triazoles 3 and 6, respectively, and is applicable
to a wide range of starting materials.
2
. Results and discussion
At first, our attention
-aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles (3) through a sequence of copper-mediated
was
turned
to
one-pot
synthesis
of
1
cross-coupling reaction of (E)-alk-1-enyldisiamylborane (1) with (trimethylsilyl)ethynyl
bromide followed by click reaction with in situ generated aryl azides. Although a lot of
2

ACCEPTED MANUSCRIPT
methods have been reported for the synthesis of 1-aryl 1,2,3-triazoles employing in situ
7
-9
generation of aryl azides, most of these methods suffer from limitations such as
prolonged heating, use of expensive ligand, substrate or solvent, use of modified copper
catalyst or unstable substrate, troublesome preparation of substrate, and low yield.
Accordingly, we chose a method where the preparation of aryl azides could be
performed by the reaction of sodium azide with arylboronic acids, which are stable‒
under air and commercially readily available, in the presence of a small amount of
8
b
Cu(OAc) in methanol under an air atmosphere at 55 ºC for 1-3 h. Thus, the
2
cross-coupling reaction of (E)-oct-1-enyldisiamylborane (1a) (1.0 mmol) with
(trimethylsilyl)ethynyl bromide (0.67 mmol) was carried out in the presence of
Cu(acac) (0.05 mmol) and NaOMe (1M, 0.75 mmol) at temperatures gradually rising
2
from –15 ºC to room temperature overnight to form (E)-dec-3-en-1-yne (2a). To the
resulting solution of 2a, phenylboronic acid (1 mmol), NaN (1.5 mmol), Cu(OAc) (0.1
3
2
mmol), and MeOH (5 mL) were added, and the reaction mixture was stirred at 55 ºC in
open air for 1.5 h in order to generate phenyl azide. After cooled to ambient temperature,
sodium ascorbate (0.1 mmol) for reduction of Cu(OAc) was added to the resultant
2
mixture, which was stirred at room temperature for 24 h (Scheme 1, eq 1). The desired
product, 1-phenyl-4-[(E)-oct-1-enyl]-1H-1,2,3-triazole (3a), was isolated in 26% yield
based on (trimethylsilyl)ethynyl bromide, indicating that the yield of the click reaction
1
4
between 2a and phenyl azide was estimated to be less than 40%. It has been
recognized that the click chemistry using copper(I)-catalyzed azide-alkyne
2
cycloaddition furnishes 1,4-disubstituted 1,2,3-triazoles in very high yields. We
surmised that incomplete formation of phenyl azide may be responsible for the low
yield of 3a. This guess led us to prepare phenyl azide in another flask from
phenylboronic acid in the same manner as described above. After phenyl azide, thus
prepared, was transferred to the flask containing 2a, sodium ascorbate (0.1 mmol) was
added to the mixture, which was stirred at room temperature for 24 h (Scheme 1, eq 2).
To our delight, the click reaction could be improved to afford 3a in 67% overall yield,
indicating that the yield of the click reaction between 2a and phenyl azide increased up
to 90%. This result ensured sufficient potential of our protocol. While all the steps could
not be carried out in a one-pot manner, each step could be performed without operation
such as exchange of solvent and filtration.
3

ACCEPTED MANUSCRIPT
Ph
N
2
Cu(acac) , 1M NaOMe
B
N
N
2
Me
3
SiC CBr
method
_
1
5 °C to r.t.
C
6
H
13-n
6
C H13-n
1
a
2a
3aa
6
C H
13-n
PhB(OH)
Cu(OAc)
2 3
, NaN
2
Na ascorbate
r.t., 24 h
one-pot method:
3aa, 26%
(1)
MeOH, 55 °C, 1.5 h, Air
3 2
NaN , Cu(OAc)
PhB(OH)
2
MeOH, 55 °C , 1.5 h, Air
PhN
3
Na ascorbate
semi-one-pot method:
3aa, 67%
(2)
r.t., 24 h
Scheme 1 Choice of the step for the preparation of phenyl azide.
Having identified the separate preparation of aryl azides from arylboronic acids as the
key step, we then explored the substrate scope of this semi-one-pot transformation using
various combinations of terminal conjugated (E)-enynes (2) and aryl azides. The results
are shown in Table 1. The semi-one-pot process mostly afforded products 3 in moderate
to good yields with excellent regio- and stereoselectivities. It should be noted that aryl
azides, prepared in another flask, could be directly used for the following click reaction
without any purification. Different compounds 2 were suitable in this transformation. In
particular, pre-chlorinated (E)-enyne, (E)-7-chlorohept-3-en-1-yne (2b), was tolerated
well (entries 15-21). A variety of aryl azides, bearing electron-donating groups such as
methoxy (entries 2, 10 and 16) and methyl (entries 3, 11, 12 and 17), and
electron-withdrawing groups such as fluoro (entries 5 and 18), acetyl (entries 6 and 19),
cyano (entriea 7 and 20) and nitro (entries 8, 14 and 21), worked well under the same
reaction conditions. The electronic effect on the phenyl ring had little influence on the
reactivity of aryl azide substrates. Unfortunately, a combination of substrates resulted in
a complex mixture which could not be separated (entries 4 and 13).
Table 1
Synthesis of 1-aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles via
a
sequence of
a
b
cross-coupling followed by click reaction
Ar
N
Cu(acac)
2
, 1M NaOMe
ArN
Na ascorbate
3 2
[ + Cu(OAc) ]
N
N
2
B
Me SiC CBr
3
R
R
1
2
3
R
c
Entry
1
R
Ar
Product
Yield (%)
67
n-C H
C H
6
3aa
6
13
5
4

ACCEPTED MANUSCRIPT
2
3
4
5
6
7
8
9
0
n-C H
4-CH OC H
3ab
69
6
13
13
13
13
13
13
13
3
6
4
n-C H
4-CH C H
3ac
3ad
3ae
3af
66
6
3
6
4
n-C H
2-CH C H
messy
65
6
3
6
4
n-C H
4-FC H
6
6
4
n-C H
3-AcC H
4
64
6
6
n-C H
3-NCC H
4
3ag
3ah
3ba
3bb
3bc
3bd
3be
3bh
3ca
3cb
3cc
3ce
3cf
58
6
6
n-C H
3-NO C H
4
65
6
2
6
C H
C H
6 5
74
6
5
5
5
5
5
5
1
C H
6
4-CH OC H
4
69
3
6
11
C H
6
4-CH C H
59
3
6
4
12
13
14
15
16
17
18
19
20
21
C H
6
2-CH C H
41
3
6
4
C H
6
4-FC H
messy
46
6
4
C H
6
3-NO C H
2 6 4
Cl(CH2)3
Cl(CH2)3
Cl(CH2)3
Cl(CH2)3
Cl(CH2)3
Cl(CH2)3
Cl(CH2)3
C H
73
6
5
4-CH OC H
4
65
3
6
4-CH C H
71
3
6
4
4-FC H
73
6
4
3-AcC H
68
6
4
3-NCC H
3cg
3ch
58
6
4
3-NO C H
4
63
2
6
a
Reaction conditions: 1 (1 mmol), Me SiC≡CBr (0.67 mmol), Cu(acac) (0.05 mmol),
3
2
1
M NaOMe (0.75 mmol), – 15 ºC to room temperature overnight under argon.
b
Reaction conditions: ArN prepared from arylboronic acid (1 mmol) and NaN (1.5
3
3
mmol) in the presence of Cu(OAc) (0.1 mmol) under air, Na ascorbate (0.1 mmol),
2
room temperature for 24 h under argon.
c
Isolated yields after silica gel column chromatography.
We next focused on broadening the scope of enynes for the π-conjugated
1
5
1
,2,3-triazole synthesis. In our previous report on the synthesis of conjugated enynes,
it was demonstrated that not only terminal conjugated (E)-enynes (2) but also
trimethysilyl-protected terminal conjugated enynes,
Z)-1,3-bis(trimethylsilyl)alk-3-en-1-ynes (5), could be prepared by copper-mediated
(
cross-coupling reaction with (trimethylsilyl)ethynyl bromide under extremely mild
conditions. Provided deprotection of the trimethylsilyl group attached to the alkyne
moiety
of
5
is
performed,
the
deprotected
compounds,
(Z)-3-(trimethylsilyl)alk-3-en-1-ynes, can participate in click reaction. It has been
5

ACCEPTED MANUSCRIPT
reported that click reaction involving a deprotection step can be also carried out in a
1
6
one-pot fashion, where tetrabutylammonium fluoride (TBAF) was frequently
employed as the desilylating reagent. Alternatively, it was found that a solution of
NaOMe in MeOH was an efficient reagent for the deprotection of the trimethylsilyl
1
5
group from 5. Our previous results as well as literature reports prompted us to
examine a two-step process involving the deprotection of 5 followed by click reaction
with
aryl
azide.
Thus,
the
cross-coupling
(4a) (1.0
reaction
mmol)
of
(
(
Z)-1-(trimethylsilyl)hex-1-enyldicyclhexylborane
with
trimethylsilyl)ethynyl bromide (0.67 mmol) was performed in the presence of CuI (0.1
mmol) and NaOH (1M, 0.75 mmol) at temperatures gradually rising from –15 ºC to
room temperature overnight to form (Z)-1,3-bis(trimethylsilyl)oct-3-en-1-yne (5a). To
the resulting solution of 5a, phenyl azide, prepared from phenylboronic acid (1 mmol),
NaN (1.5 mmol), and Cu(OAc) (0.1 mmol) in MeOH (5 mL) at 55 ºC in open air for
3
2
1
.5 h, was added, followed by addition of sodium ascorbate (0.1 mmol) and NaOMe (1
M, 1 mmol). The reaction mixture was stirred at room temperature for 24 h (Eq. 1). We
were pleased to find that the two steps proceeded smothly at the same time to afford the
desired product, 1-phenyl-4-[(Z)-1-(trimethylsilyl)hex-1-enyl]-1H-1,2,3-triazole (6a), in
6
0% isolated yield based on (trimethylsilyl)ethynyl bromide. The geometry of 6a was
1
7
assigned by using desilylation of alkenylsilanes with retention of the double bond.
1
8
Protodesilylation of 6a with HI gave 1-phenyl-4-[(E)-hex-1-enyl]-1H-1,2,3-triazole as
the sole product, thus demonstrating Z-configuration of 6a (Eq. 2).
3 2
PhN [ + Cu(OAc) ]
Na ascorbate
1M NaOMe
Ph
N
CuI, 1M NaOH
N
N
2
B
Me
3
SiC CBr
3
Me Si
(1)
_1
5 °C to r.t.
r.t., 24 h
Me
3
Si
C
H
9
-n
Me
3
Si
5a
4 9
C H -n
4
4a
Me
3
Si
4 9
C H -n
6a 60%
Ph
N
Ph
N
N
N
N
N
HI
(2)
Me
3
Si
C
4
H
9
-n
4 9
C H -n
6a
To evaluate the scope of this semi-one-pot transformation, various combinations of
(Z)-1,3-bis(trimethylsilyl)alk-3-en-1-ynes (5) and aryl azides were used. The reactions
were conducted under the conditions described above, and the results are shown in
Table
2.
The
semi-one-pot
process
afforded
exclusively in
1
-aryl-4-[(Z)-1-(trimethylsilyl)alk-1-enyl]-1H-1,2,3-triazoles
(6)
moderate to good yields. In this process, aryl azides, prepared in another flask, could be
also used without any purification. It is noteworthy that such functional groups as acetyl,
6

ACCEPTED MANUSCRIPT
cyano, and nitro on the phenyl ring of aryl azides were tolerated under basic conditions.
However, the products bearing cyano group (entries 7 and 15) were obtained in lower
yields compared with those bearing the other two functional groups (entries 6, 8, 14 and
1
6). The reaction with 2-methylphenyl azide resulted in low product yields (entries 4
and 12), probably due to steric hindrance. It is interesting to note that the use of NaOMe
as the desilylating reagent afforded products 6 in higher yields than that of TBAF
(entries 1, 8 and 9).
Table 2
Synthesis of 1-aryl-4-[(Z)-1-(trimethylsilyl)alk-1-enyl]-1H-1,2,3-triazoles via
a
a
b
sequence of cross-coupling followed by desilylation/click reaction
3 2
ArN [ + Cu(OAc) ]
Na ascorbate
1M NaOMe
Ar
N
CuI, NaOH
N
N
2
B
Me SiC CBr
3
Me Si
3
Me
3
Si
R
Me Si
R
3
Me
3
Si
R
4
5
6
c
Entry
R
Ar
Product
6aa
6ab
6ac
Yield (%)
d
1
2
3
4
5
6
7
8
9
0
n-C H9
C H
6
60 (45)
4
5
n-C H9
4-CH OC H
4
63
68
32
65
62
30
4
3
6
n-C H9
4-CH C H
3 6
4
4
n-C H9
2-CH C H
6ad
6ae
4
3
6
4
n-C H9
4-FC H
4
6
4
n-C H9
3-AcC H
4
6af
4
6
n-C H9
3-NCC H
4
6ag
6ah
6ba
6bb
6bc
6bd
6be
6bf
4
6
d
n-C H9
3-NO C H
4
58 (42)
4
2
6
d
C H
C H
6 5
54 (44)
6
5
5
5
5
5
5
5
5
1
C H
4-CH OC H
4
61
53
40
52
58
39
55
6
3
6
11
C H
4-CH C H
3 6
6
4
12
13
14
15
16
C H
2-CH C H
6
3
6
4
C H
4-FC H
6
6
4
C H
3-AcC H
6 4
6
C H
3-NCC H
4
6bg
6bh
6
6
C H
3-NO C H
2 6 4
6
a
Reaction conditions: 4 (1 mmol), Me SiC≡CBr (0.67 mmol), CuI (0.1 mmol), 1M or
3
2
M NaOH (0.75 mmol), – 15 ºC to room temperature overnight under argon.
b
Reaction conditions: ArN prepared from arylboronic acid (1 mmol) and NaN (1.5
3
3
mmol) in the presence of Cu(OAc) (0.1 mmol) under air, Na ascorbate (0.1 mmol),
2
7

ACCEPTED MANUSCRIPT
1
M NaOMe (1 mmol), room temperature for 24 h under argon.
c
Isolated yields after silica gel column chromatography.
d
1
M TBAF (2 mmol) was used instead of 1M NaOMe (1 mmol).
3
. Conclusion
In conclusion, we have reported a practical and general method for the synthesis of
not
only
1-aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles
but
also
a
1
-aryl-4-[(Z)-1-(trimethylsilyl)alk-1-enyl]-1H-1,2,3-triazoles
through
cross-coupling/click reaction sequence. To the best of our knowledge, the present
protocol represents the first example of constructing a series of π-extended
1
,2,3-triazoles with both an aryl moiety at the 1-position and a geometricaldefined
alkenyl moiety at the 4-positin on the triazole ring. This approach uses simple and
readily available starting materials and shows good functional compatibility. The
procedure can be successfully performed without isolation and purification of any
compounds during the process, albeit in a semi-one-pot manner. These features make
this protocol potentially attractive for the synthesis of the π-extended 1,2,3-triazoles.
4
. Experimental
4
.1. General information
NMR spectra were recorded on JEOL JNM-A-500 or JEOL JNM-ECA-600
spectrometer. Chemical shifts are quoted in parts per million (ppm) downfield of TMS.
Coupling constants J are quoted in Hz. IR spectra were recorded on a Shimadzu FT-IR
8
300 spectrometer, and only the strongest/structurally most important absorption peaks
are listed. Electrospray ionization (ESI) HRMS analyses were measured on a Thermo
Scientific Exactive instrument. Melting points were determined on a Yamato MP-21 and
are uncorrected. TLC analyses were carried out using aluminium sheets pre-coated with
silica gel 60 F254 purchased from Merck. Product purification was performed by column
chromatography using silica gel 60 (Kanto Chemical, 63-210 ꢀm). Unless otherwise
noted, commercially available materials were used without any purification. Alk-1-yne,
2
-methylbut-2-ene, and cyclohexene were used after distillation over CaH under argon.
2
1
-(Trimethylsilyl)alk-1-ynes were used after distillation under argon. THF was distilled
from Na-benzophenone ketyl under argon before use. Borane dimethyl sulfide complex
(
BH ·SMe ) was purchased from Aldrich. (Trimethylsilyl)ethynyl bromide was
3
2
1
9
prepared according to the literature procedure.
8

ACCEPTED MANUSCRIPT
4
.2. General
procedure
for
the
synthesis
of
1
-aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles
A 25 mL round-bottomed flask was charged with a solution of BH ·SMe (1 mmol)
3
2
in THF (3 mL) under an argon atmosphere. To the solution was added
2
-methylbut-2-ene (0.14 g, 2 mmol) dropwise at – 15 ºC, and the reaction mixture was
2
0
stirred for 2 h at room temperature to form a solution of disiamylborane in THF. To
this solution was added alk-1-yne (1 mmol) dropwise at – 15 ºC, and the mixture was
stirred for 2 h at 0 ºC. A solution of (E)-alk-1-enyldisiamylborane 1 (1 mmol) in THF,
thus prepared, was cooled to – 15 ºC, and Cu(acac) (0.013 g, 0.05 mmol) was added to
2
the solution under a flow of argon, followed by dropwise addition of
(trimethylsilyl)ethynyl bromide (0.119 g, 0.67 mmol) and NaOMe (1M, 0.75 mL, 0.75
mmol). The resulting mixture was allowed to warm gradually to room temperature and
stirred overnight to form (E)-alk-3-en-1-yne 2. In another 25 mL round-bottomed flask,
aryl azide was prepared by using arylboronic acid (1 mmol), NaN (0.098 g, 1.5 mmol),
3
Cu(OAc) (0.018 g, 0.1 mmol) and MeOH (5 mL). Thus, the mixture was stirred at 55
2
8
b
ºC for 1.5-3.0 h under aerobic condition. To the flask containing (E)-alk-3-en-1-yne 2
was transferred a dark brown suspension of aryl azide in MeOH, and (+)-sodium
L-ascorbate (0.02 g, 0.1 mmol) was added to the mixture under a flow of argon. The
resulting mixture was stirred at room temperature for 24 h and then treated by bubbling
air through the solution with tube pump at room temperature for 2 h to oxidize the
residual organoboron compound. The mixture was extracted with EtOAc (3 × 10 mL),
washed with brine (10 mL), dried (Na SO ), and filtered. The solvent was evaporated
2
4
under reduced pressure and the residue was purified by column chromatography on
silica gel to give product 3.
4
.3. General
procedure
for
the
synthesis
of
1
-aryl-4-[(Z)-1-(trimethylsilyl)alk-1-enyl]-1H-1,2,3-triazoles
A 25 mL round-bottomed flask was charged with a solution of BH ·SMe (1 mmol)
3
2
in THF (3 mL) under an argon atmosphere. To the solution was added cyclohexene
(
0.164 g, 2 mmol) dropwise at 0 ºC, and the reaction mixture was stirred for 2 h at this
2
0
temperature to form a white suspension of dicyclohexylborane in THF. To this
suspension was added 1-(trimethylsilyl)alk-1-yne (1 mmol) dropwise at 0 ºC, and the
mixture was stirred for 2 h at this temperature to produce a clear solution of
9

ACCEPTED MANUSCRIPT
(Z)-1-(trimethylsilyl)alk-1-enyldicyclohexylborane 4 in THF. This solution was cooled
to – 15 ºC, and CuI (0.019 g, 0.1 mmol) was added to the solution under a flow of argon,
followed by dropwise addition of (trimethylsilyl)ethynyl bromide (0.119 g, 0.67 mmol)
and NaOH (1M, 0.75 mL for 4a or 2M, 0.375 mL for 4b, 0.75 mmol). The resulting
mixture was allowed to warm gradually to room temperature and stirred overnight to
form (Z)-1,3-bis(trimethylsilyl)alk-3-en-1-yne 5. In another 25 mL round-bottomed
flask, aryl azide was prepared as described in general procedure for the synthesis of
1
-aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles.
Z)-1,3-bis(trimethylsilyl)alk-3-en-1-yne 5 was transferred a dark brown suspension of
aryl azide in MeOH, and (+)-sodium -ascorbate (0.02 g, 0.1 mmol) was added to the
To
the
flask
containing
(
L
mixture under a flow of argon, followed by addition of NaOMe (1M, 1.0 mL, 1.0 mmol).
The resulting mixture was stirred at room temperature for 24 h and worked up as
described in
-aryl-4-[(E)-alk-1-enyl]-1H-1,2,3-triazoles. Product 6 was isolated by column
chromatography on silica gel.
a
typical experimental procedure for the synthesis of
1
4
.4. Characterization of the products
4
.4.1. 4-[(E)-Oct-1-enyl]-1-phenyl-1H-1,2,3-triazole (3aa). Light-brown solid,
1
hexane-EtOAc (7:3) as eluent, mp. 58-59 ºC. H NMR (500 MHz, CDCl ): δ = 0.89 (t, J
3
=
6.8 Hz, 3H), 1.26-1.40 (m, 6H), 1.45-1.53 (m, 2H), 2.21-2.27 (m, 2H), 6.45 (d, J =
1
7
6.1 Hz, 1H), 6.52 (dt, J = 16.1 and 6.8 Hz, 1H), 7.40-7.45 (m, 1H), 7.49-7.54 (m, 2H),
1
3
.70-7.75 (m, 2H), 7.86 (s, 1H). C NMR (125 MHz, CDCl ): δ = 14.1 (CH ), 22.6
3
3
(
CH ), 28.8 (CH ), 28.9 (CH ), 31.7 (CH ), 32.9 (CH ), 117.4 (=CH), 117.8 (=CH),
2 2 2 2 2
1
1
7
2
20.4 (2 × CHarom), 128.5 (CHarom), 129.7 (2 × CHarom), 134.6 (=CH), 137.0 (Carom),
47.1 (=C). IR (KBr): ν = 3132, 2923, 2854, 1598, 1504, 1465, 1234, 1217, 1045, 977,
ꢀ
1
+
56, 684 cm . HRMS (ESI): m/z [M + Na] calcd for C H N Na: 278.1626; found
1
6
21
3
78.1630.
4
.4.2. 1-(4-Methoxyphenyl)-4-[(E)-oct-1-enyl]-1H-1,2,3-triazole (3ab). Off-white solid,
1
hexane-EtOAc (7:3) as eluent, mp. 57-58 ºC. H NMR (600 MHz, CDCl ): δ = 0.89 (t, J
3
=
6.8 Hz, 3H), 1.26-1.39 (m, 6H), 1.45-1.51 (m, 2H), 2.20-2.25 (m, 2H), 6.43 (d, J =
1
7
2
6.1 Hz, 1H), 6.48 (dt, J = 16.1 and 6.8 Hz, 1H), 6.97-7.02 (m, 2H), 7.58-7.63 (m, 2H),
1
3
.77 (s, 1H). C NMR (150 MHz, CDCl ): δ = 14.1 (CH ), 22.6 (CH ), 28.8 (CH ),
3
3
2
2
9.0 (CH ), 31.7 (CH ), 32.9 (CH ), 55.6 (CH ), 114.7 (2 × CHarom), 117.5 (=CH), 118.0
2
2
2
3
(=CH), 122.0 (2 × CHarom), 130.5 (Carom), 134.2 (=CH), 146.9 (=C), 159.6 (Carom). IR
10

ACCEPTED MANUSCRIPT
ꢀ
1
(
KBr): ν = 3122, 2923, 2856, 1519, 1251, 1232, 1043, 970, 833 cm . HRMS (ESI): m/z
+
[
M + Na] calcd for C H ON Na: 308.1731; found 308.1732.
1
7
23
3
4
.4.3. 1-(4-Methylphenyl)-4-[(E)-oct-1-enyl]-1H-1,2,3-triazole (3ac). White solid,
1
hexane-EtOAc (7:3) as eluent, mp. 77-78 ºC. H NMR (500 MHz, CDCl ): δ = 0.89 (t, J
3
=
6.8 Hz, 3H), 1.25-1.40 (m, 6H), 1.45-1.53 (m, 2H), 2.19-2.27 (m, 2H), 2.41 (s, 3H),
6
7
.44 (d, J = 16.1 Hz, 1H), 6.50 (dt, J = 16.1 and 6.3 Hz, 1H), 7.27-7.32 (m, 2H),
1
3
.57-7.62 (m, 2H), 7.82 (s, 1H). C NMR (125 MHz, CDCl ): δ = 14.1 (CH ), 21.0
3
3
(
CH ), 22.6 (CH ), 28.8 (CH ), 28.9 (CH ), 31.7 (CH ), 32.9 (CH ), 117.3 (=CH), 117.8
3 2 2 2 2 2
(=CH), 120.2 (2 × CHarom), 130.1 (2 × CHarom), 134.4 (=CH), 134.7 (Carom), 138.6
(
Carom), 146.9 (=C). IR (KBr): ν = 3122, 2923, 2854, 1519, 1232, 1217, 1041, 975, 817,
ꢀ
1
+
7
38 cm . HRMS (ESI): m/z [M + Na] calcd for C H N Na: 292.1782; found
17 23 3
2
92.1781.
4
.4.4. 1-(4-Fluorophenyl)-4-[(E)-oct-1-enyl]-1H-1,2,3-triazole (3ae). Light-brown solid,
1
hexane-EtOAc (7:3) as eluent, mp. 71-73 ºC. H NMR (500 MHz, CDCl ): δ = 0.89 (t, J
3
=
6.8 Hz, 3H), 1.23-1.42 (m, 6H), 1.44-1.53 (m, 2H), 2.18-2.28 (m, 2H), 6.43 (d, J =
1
7
2
6.1 Hz, 1H), 6.51 (dt, J = 16.1 and 6.3 Hz, 1H), 7.15-7.25 (m, 2H), 7.65-7.75 (m, 2H),
1
3
.82 (s, 1H). C NMR (125 MHz, CDCl ): δ = 14.1 (CH ), 22.6 (CH ), 28.9 (CH ),
3
3
2
2
8.9 (CH ), 31.7 (CH ), 32.9 (CH ), 116.6 (d, J = 23.7 Hz, 2 × CHarom), 117.5 (=CH),
2
2
2
117.7 (=CH), 122.3 (d, J = 8.2 Hz, 2 × CHarom), 133.3 (CHarom), 134.6 (=CH), 147.2
(
=C), 162.2 (d, J = 248.3 Hz, Carom). IR (KBr): ν = 3124, 2925, 2856, 1519, 1224, 1041,
ꢀ
1
+
9
77, 839, 742 cm . HRMS (ESI): m/z [M + Na] calcd for C H N FNa: 296.1532;
16 20 3
found 296.1531.
4
.4.5. 1-(3-Acetoxyphenyl)-4-[(E)-oct-1-enyl]-1H-1,2,3-triazole (3af). Off-white solid,
1
hexane-EtOAc (7:3) as eluent, mp. 56-57 ºC. H NMR (500 MHz, CDCl ): δ = 0.89 (t, J
3
=
6.8 Hz, 3H), 1.25-1.40 (m, 6H), 1.44-1.53 (m, 2H), 2.20-2.27 (m, 2H), 2.66 (s, 3H),
6
7
1
.44 (d, J = 16.1 Hz, 1H), 6.53 (dt, J = 16.1 and 8.3 Hz, 1H), 7.61 (t, J = 7.8 Hz, 1H),
1
3
.96-8.02 (m, 2H), 8.01 (s, 1H), 8.25-8.28 (m, 1H). C NMR (125 MHz, CDCl ): δ =
3
3.9 (CH ), 22.4 (CH ), 26.5 (CH ), 28.6 (CH ), 28.7 (CH ), 31.5 (CH ), 32.7 (CH ),
3
2
3
2
2
2
2
1
17.1 (=CH), 117.4 (=CH), 119.1 (CHarom), 124.2 (CHarom), 128.0 (CHarom), 129.9
CHarom), 134.8 (=CH), 137.1 (Carom), 138.1 (Carom), 147.1 (=C), 196.5 (C=O). IR (KBr):
ν = 3134, 2925, 2854, 1674, 1593, 1504, 1454, 1267, 1215, 1043, 968, 893, 806, 682
(
ꢀ
1
+
cm . HRMS (ESI): m/z [M + Na] calcd for C H ON Na: 320.1731; found 320.1730.
1
8
23
3
11

ACCEPTED MANUSCRIPT
4
.4.6. 1-(3-Cyanophenyl)-4-[(E)-oct-1-enyl]-1H-1,2,3-triazole (3ag). White solid,
1
hexane-EtOAc (7:3) as eluent, mp. 52-53 ºC. H NMR (500 MHz, CDCl ): δ = 0.89 (t, J
3
=
6.8 Hz, 3H), 1.26-1.40 (m, 6H), 1.46-1.53 (m, 2H), 2.22-2.28 (m, 2H), 6.44 (dt, J =
1
1
6.1 and 1.4 Hz, 1H), 6.56 (dt, J = 16.1 and 6.8 Hz, 1H), 7.64-7.74 (m, 2H), 7.89 (s,
1
3
H), 8.01-8.07 (m, 2H). C NMR (125 MHz, CDCl ): δ = 14.0 (CH ), 22.5 (CH ), 28.8
3
3
2
(
CH ), 28.8 (CH ), 31.6 (CH ), 32.9 (CH ), 114.0 (Carom), 116.8 (=CH), 117.2 (=CH),
2 2 2 2
117.4 (≡C), 123.2 (CHarom), 124.1 (CHarom), 130.8 (CHarom), 131.7 (CHarom), 135.5
(
=CH), 137.5 (Carom), 147.6 (=C). IR (KBr): ν = 3130, 2925, 2854, 2235, 1587, 1487,
ꢀ
1
+
1
217, 1043, 972, 893, 804, 680, 667 cm . HRMS (ESI): m/z [M + Na] calcd for
C H N Na: 303.1580; found 303.1579.
17
20
4
4
.4.7. 1-(3-Nitrophenyl)-4-[(E)-oct-1-enyl]-1H-1,2,3-triazole (3ah). Light-yellow solid,
1
hexane-EtOAc (7:3) as eluent, mp. 80-81 ºC. H NMR (600 MHz, CDCl ): δ = 0.89 (t, J
3
=
6.8 Hz, 3H), 1.27-1.44 (m, 6H), 1.46-1.53 (m, 2H), 2.22-2.28 (m, 2H), 6.45 (d, J =
1
8
5.8 Hz, 1H), 6.57 (dt, J = 15.8 and 6.8 Hz, 1H), 7.74 (t, J = 8.2 Hz, 1H), 7.98 (s, 1H),
1
3
.17-8.21 (m, 1H), 8.26-8.30 (m, 1H), 8.57 (t, J = 2.0 Hz, 1H). C NMR (150 MHz,
CDCl ): δ = 14.1 (CH ), 22.6 (CH ), 28.8 (CH ), 28.9 (CH ), 31.7 (CH ), 33.0 (CH ),
3
3
2
2
2
2
2
114.9 (CHarom), 117.0 (=CH), 117.3 (=CH), 122.9 (CHarom), 125.7 (CHarom), 130.9
(
CHarom), 135.6 (=CH), 137.8 (Carom), 147.8 (=C), 148.9 (Carom). IR (KBr): ν = 3143,
ꢀ
1
2
920, 2852, 1541, 1348, 1265, 1043, 966, 885, 800, 734, 704 cm . HRMS (ESI): m/z
+
[
M + Na] calcd for C H O N Na: 323.1478; found 323.1479.
1
6
20
2
4
4
.4.8. 1-Phenyl-4-[(E)-2-phenylethenyl]-1H-1,2,3-triazole (3ba). Off-white solid,
1
hexane-EtOAc (7:3) as eluent, mp. 149-150 ºC. H NMR (600 MHz, CDCl ): δ = 7.15
3
(
d, J = 16.5 Hz, 1H), 7.26-7.31 (m, 1H), 7.34-7.40 (m, 2H), 7.42 (d, J = 16.5 Hz, 1H),
1
3
7
.42-7.47 (m, 1H), 7.50-7.56 (m, 4H), 7.73-7.78 (m, 2H), 8.01 (s, 1H). C NMR (150
MHz, CDCl ): δ = 116.2 (=CH), 118.2 (=CH), 120.4 (2 × CHarom), 126.5 (2 × CHarom),
3
1
1
28.1 (CHarom), 128.7 (2 × CHarom), 129.7 (2 × CHarom), 131.3 (=CH), 136.6 (Carom),
ꢀ
1
36.9 (Carom), 146.8 (=C). IR (KBr): ν = 3130, 1504, 1232, 1043, 964, 756, 688 cm .
+
HRMS (ESI): m/z [M + Na] calcd for C H N Na: 270.1001; found 270.1001.
1
6
13
3
4
.4.9. 1-(4-Methoxyphenyl)-4-[(E)-2-phenylethenyl]-1H-1,2,3-triazole (3bb). White
1
solid, hexane-EtOAc (7:3) as eluent, mp. 153-154 ºC. H NMR (600 MHz, DMSO-d ):
6
δ = 3.84 (s, 3H), 7.14-7.18 (m, 2H), 7.26 (d, J = 16.5 Hz, 1H), 7.28-7.32 (m, 1H), 7.37
(
d, J = 16.5 Hz, 1H), 7.38-7.42 (m, 2H), 7.60-7.64 (m, 2H), 7.81-7.85 (m, 2H), 8.87 (s,
1
3
1
H). C NMR (150 MHz, DMSO-d ): δ = 55.5 (CH ), 114.8 (2 × CHarom), 117.0 (=CH),
6 3
12

ACCEPTED MANUSCRIPT
119.9 (=CH), 121.5 (2 × CHarom), 126.3 (2 × CHarom), 127.8 (CHarom), 128.7 (2 ×
CHarom), 129.9 (Carom), 130.0 (=CH), 136.4 (Carom), 145.9 (=C), 159.2 (Carom). IR (KBr):
ꢀ
1
ν = 3118, 1515, 1245, 1232, 1035, 1026, 962, 833, 815, 750, 704, 692 cm . HRMS
+
(
ESI): m/z [M + Na] calcd for C H ON Na: 300.1107; found 300.1106.
1
7
15
3
4
.4.10. 1-(4-Methylphenyl)-4-[(E)-2-phenylethenyl]-1H-1,2,3-triazole (3bc). Off-white
1
solid, hexane-EtOAc (7:3) as eluent, mp. 156-157 ºC. H NMR (500 MHz, CDCl ): δ =
3
2
7
2
.42 (s, 3H), 7.14 (d, J = 16.6 Hz, 1H), 7.25-7.40 (m, 5H), 7.41 (d, J = 16.6 Hz, 1H),
1
3
.49-7.54 (m, 2H), 7.60-7.65 (m, 2H), 7.98 (s, 1H). C NMR (125 MHz, CDCl ): δ =
3
1.1 (CH ), 116.2 (=CH), 118.3 (=CH), 120.3 (2 × CHarom), 126.5 (2 × CHarom), 128.0
3
(CHarom), 128.7 (2 × CHarom), 130.2 (2 × CHarom), 131.3 (=CH), 134.6 (Carom), 136.6
(
Carom), 138.9 (Carom), 146.5 (=C). IR (KBr): ν = 3120, 1517, 1215, 962, 839, 767, 750,
ꢀ
1
+
6
94 cm . HRMS (ESI): m/z [M + Na] calcd for C H N Na: 284.1158; found
17 15 3
2
84.1157.
4
.4.11. 1-(2-Methylphenyl)-4-[(E)-2-phenylethenyl]-1H-1,2,3-triazole (3bd). Off-white
1
solid, hexane-EtOAc (7:3) as eluent, mp. 106-107 ºC. H NMR (600 MHz, CDCl ): δ =
3
2
.25 (s, 3H), 7.17 (d. J = 16.1 Hz, 1H), 7.26-7.31 (m, 1H), 7.32-7.48 (m, 7H), 7.51-7.55
1
3
(m, 2H), 7.76 (s, 1H). C NMR (150 MHz, CDCl ): δ = 17.9 (CH ), 116.3 (=CH),
3 3
1
21.9 (=CH), 125.9 (CHarom), 126.5 (2 × CHarom), 126.8 (CHarom), 128.0 (CHarom), 128.7
(
2 × CHarom), 129.8 (CHarom), 131.0 (CHarom), 131.5 (=CH), 133.6 (Carom), 136.4 (Carom),
ꢀ
1
1
36.7 (Carom), 145.9 (=C). IR (KBr): ν = 3134, 1504, 1041, 966, 761, 707, 692 cm .
+
HRMS (ESI): m/z [M + Na] calcd for C H N Na: 284.1158; found 284.1158.
1
7
15
3
4
.4.12. 1-(3-Nitrophenyl)-4-[(E)-2-phenylethenyl]-1H-1,2,3-triazole (3bh). Yellow solid,
1
hexane-EtOAc (7:3) as eluent, mp. 124-125 ºC. H NMR (600 MHz, CDCl ): δ = 7.16
3
(d, J = 16.5 Hz, 1H), 7.30-7.34 (m, 1H), 7.37-7.42 (m, 2H), 7.48 (d, J = 16.5 Hz, 1H),
7
.53-7.57 (m, 2H), 7.77 (t, J = 8.2 Hz, 1H), 8.12 (s, 1H), 8.22-8.25 (m, 1H), 8.30-8.33
1
3
(m, 1H), 8.62 (t, J = 2.0 Hz, 1H). C NMR (150 MHz, DMSO-d ): δ = 114.4 (CHarom),
6
116.5 (=CH), 120.3 (=CH), 122.9 (CHarom), 125.8 (CHarom), 126.4 (2 × CHarom), 128.0
(CHarom), 128.7 (2 × CHarom), 130.7 (=CH), 131.5 (CHarom), 136.1 (Carom), 137.0 (Carom),
1
46.4 (=C), 148.4 (Carom). IR (KBr): ν = 3139, 3085, 1537, 1494, 1346, 1217, 1045, 968,
ꢀ
1
+
8
83, 871, 798, 748, 734, 702, 686, 669 cm . HRMS (ESI): m/z [M + Na] calcd for
C H O N Na: 315.0854; found 315.0855.
16
12
2
4
4
.4.13. 4-[(E)-5-Chloropent-1-enyl]-1-phenyl-1H-1,2,3-triazole (3ca). Off-white solid,
13

ACCEPTED MANUSCRIPT
1
hexane-EtOAc (7:3) as eluent, mp. 69-70 ºC. H NMR (500 MHz, CDCl ): δ =
3
1
.92-2.00 (m, 2H), 2.37-2.44 (m, 2H), 3.59 (t, J = 6.8 Hz, 2H), 6.84-6.51 (m, 2H),
1
3
7
.40-7.44 (m, 1H), 7.48-7.53 (m, 2H), 7.70-7.74 (m, 2H), 7.88 (s, 1H). C NMR (125
MHz, CDCl ): δ = 29.9 (CH ), 31.6 (CH ), 44.2 (CH ), 117.7 (=CH), 119.2 (=CH),
3
2
2
2
1
1
20.3 (2 × CHarom), 128.6 (CHarom), 129.7 (2 × CHarom), 131.8 (=CH), 136.9 (Carom),
ꢀ
1
46.5 (=C). IR (KBr): ν = 3122, 2956, 1598, 1504, 1230, 1045, 970, 759, 688 cm .
+
HRMS (ESI): m/z [M + Na] calcd for C H N ClNa: 270.0768; found 270.0768.
1
3
14
3
4
.4.14. 4-[(E)-5-Chloropent-1-enyl]-1-(4-methoxyphenyl)-1H-1,2,3-triazole (3cb).
1
Off-white solid, hexane-EtOAc (7:3) as eluent, mp. 76-77 ºC. H NMR (600 MHz,
CDCl ): δ = 1.94-2.00 (m, 2H), 2.38-2.44 (m, 2H), 3.59 (t, J = 6.8 Hz, 2H), 3.86 (s, 3H),
3
1
3
6
.44-6.52 (m, 2H), 6.99-7.03 (m, 2H), 7.59-7.63 (m, 2H), 7.78 (s, 1H). C NMR (150
MHz, CDCl ): δ = 29.9 (CH ), 31.7 (CH ), 44.2 (CH ), 55.6 (CH ), 114.7 (2 × CHarom),
3
2
2
2
3
117.9 (=CH), 119.3 (=CH), 122.0 (2 × CHarom), 130.4 (Carom), 131.7 (=CH), 146.3 (=C),
1
8
3
59.7 (Carom). IR (KBr): ν = 3132, 2958, 2839, 1519, 1257, 1218, 1110, 1028, 970, 837,
ꢀ
1
+
15 cm . HRMS (ESI): m/z [M + Na] calcd for C H ON ClNa: 300.0874; found
14
16
3
00.0872.
4
.4.15.
4-[(E)-5-Chloropent-1-enyl]-1-(4-methylphenyl)-1H-1,2,3-triazole
(3cc).
1
Off-white solid, hexane-EtOAc (7:3) as eluent, mp. 80-81 ºC. H NMR (500 MHz,
CDCl ): δ = 1.92-1.99 (m, 2H), 2.36-2.43 (m, 2H), 2.40 (s, 3H), 3.58 (t, J = 6.8 Hz, 2H),
3
1
3
6
.47-6.50 (m, 2H), 7.26-7.31 (m, 2H), 7.56-7.61 (m, 2H), 7.86 (s, 1H). C NMR (125
MHz, CDCl ): δ = 20.9 (CH ), 29.8 (CH ), 31.5 (CH ), 44.1 (CH ), 117.6 (=CH), 119.0
3
3
2
2
2
(=CH), 120.1 (2 × CHarom), 130.0 (2 × CHarom), 131.7 (=CH), 134.5 (Carom), 138.6
(
Carom), 146.1 (=C). IR (KBr): ν = 3149, 3049, 2925, 1515, 1444, 1265, 1230, 1045, 968,
ꢀ
1
+
8
2
17, 746 cm . HRMS (ESI): m/z [M + Na] calcd for C H N ClNa: 284.0924; found
14 16 3
84.0923.
4
.4.16.
4-[(E)-5-Chloropent-1-enyl]-1-(4-fluorophenyl)-1H-1,2,3-triazole
(3ce).
1
Off-white solid, hexane-EtOAc (7:3) as eluent, mp. 80-82 ºC. H NMR (500 MHz,
CDCl ): δ = 1.91-2.00 (m, 2H), 2.36-2.44 (m, 2H), 3.59 (t, J = 6.3 Hz, 2H), 6.46-6.50
3
1
3
(
m, 2H), 7.16-7.23 (m, 2H), 7.66-7.73 (m, 2H), 7.87 (s, 1H). C NMR (125 MHz,
CDCl ): δ = 29.9 (CH ), 31.6 (CH ), 44.3 (CH ), 116.6 (d, J = 22.7 Hz, 2 × CHarom),
3
2
2
2
117.9 (=CH), 119.1 (=CH), 122.3 (d, J = 9.3 Hz, 2 × CHarom), 132.0 (=CH), 133.2 (d, J
=
2.0 Hz, Carom), 146.6 (=C), 162.2 (d, J = 249.3 Hz, Carom). IR (KBr): ν = 3126, 1504,
ꢀ
1
+
1
444, 1230, 1197, 1047, 972, 833, 744 cm . HRMS (ESI): m/z [M + Na] calcd for
14

ACCEPTED MANUSCRIPT
C H N FClNa: 288.0674; found 288.0673.
13
13
3
4
.4.17.
1-(3-Acetoxyphenyl)-4-[(E)-5-chloropent-1-enyl]-1H-1,2,3-triazole
(3cf).
1
Off-white solid, hexane-EtOAc (7:3) as eluent, mp. 90-91 ºC. H NMR (600 MHz,
CDCl ): δ = 1.95-2.02 (m, 2H), 2.40-2.47 (m, 2H), 2.68 (s, 3H), 3.61 (t, J = 6.8 Hz, 2H),
3
6
7
.52 (d, J = 16.5 Hz, 1H), 6.54 (dt, J = 16.5 and 6.2 Hz, 1H), 7.65 (t, J = 7.8 Hz, 1H),
1
3
.97 (s, 1H), 7.99-8.04 (m, 2H), 8.27 (br s, 1H). C NMR (150 MHz, CDCl ): δ = 26.7
3
(
CH ), 29.9 (CH ), 31.6 (CH ), 44.2 (CH ), 117.6 (=CH), 118.9 (=CH), 119.4 (CHarom),
3 2 2 2
1
24.6 (CHarom), 128.3 (CHarom), 130.2 (CHarom), 132.5 (=CH), 137.3 (Carom), 138.4
(
Carom), 146.8 (=C), 196.7 (C=O). IR (KBr): ν = 3128, 2937, 1681, 1591, 1494, 1450,
ꢀ
1
+
1
359, 1265, 1045, 999, 966, 792, 686 cm . HRMS (ESI): m/z [M + Na] calcd for
C H ON ClNa: 312.0874; found 312.0875.
15
16
3
4
.4.18.
4-[(E)-5-Chloropent-1-enyl]-1-(3-cyanophenyl)-1H-1,2,3-triazole
(3cg).
1
Light-brown solid, hexane-EtOAc (7:3) as eluent, mp. 62-63 ºC. H NMR (600 MHz,
CDCl ): δ = 1.95-2.02 (m, 2H), 2.41-2.47 (m, 2H), 3.61 (t, J = 6.8 Hz, 2H), 6.50 (d, J =
3
1
6.5 Hz, 1H), 6.55 (dt, J = 16.5 and 6.8 Hz, 1H), 7.67 (t, J = 7.3 Hz, 1H), 7.71-7.75 (m,
1
3
1
H), 7.90 (s, 1H), 8.01-8.05 (m, 1H), 8.05-8.07 (m, 1H). C NMR (150 MHz, CDCl ):
3
δ = 29.9 (CH ), 31.5 (CH ), 44.2 (CH ), 114.1 (Carom), 117.2 (=CH), 117.4 (≡C), 118.7
2
2
2
(=CH), 123.3 (CHarom), 124.2 (CHarom), 130.9 (CHarom), 131.9 (CHarom), 132.9 (=CH),
1
7
2
37.5 (Carom), 147.1 (=C). IR (KBr): ν = 3134, 2233, 1587, 1487, 1444, 1043, 999, 966,
ꢀ
1
+
94, 680 cm . HRMS (ESI): m/z [M + Na] calcd for C H N ClNa: 295.0722; found
1
4
13
4
95.0723.
4
.4.19.
4-[(E)-5-Chloropent-1-enyl]-1-(3-nitrophenyl)-1H-1,2,3-triazole
(3ch).
1
Light-yellow solid, hexane-EtOAc (7:3) as eluent, mp. 100-101 ºC. H NMR (600 MHz,
CDCl ): δ = 1.96-2.02 (m, 2H), 2.42-2.48 (m, 2H), 3.61 (t, J = 6.8 Hz, 2H), 6.51 (d, J =
3
1
8
6.4 Hz, 1H), 6.57 (dt, J = 16.4 and 6.8 Hz, 1H), 7.75 (t, J = 8.2 Hz, 1H), 8.00 (s, 1H),
1
3
.18-8.21 (m, 1H), 8.28-8.31 (m, 1H), 8.58 (t, J = 2.0 Hz, 1H). C NMR (150 MHz,
CDCl ): δ = 29.9 (CH ), 31.6 (CH ), 44.2 (CH ), 114.9 (CHarom), 117.3 (=CH), 118.6
3
2
2
2
(=CH), 123.0 (CHarom), 125.7 (CHarom), 131.0 (=CH), 133.0 (CHarom), 137.6 (Carom),
1
8
3
47.2 (=C), 148.9 (Carom). IR (KBr): ν = 3151, 3093, 1537, 1494, 1346, 1224, 1047, 964,
ꢀ
1
+
83, 871, 798, 734, 669 cm . HRMS (ESI): m/z [M + Na] calcd for C H O N ClNa:
13
13
2
4
15.0620; found 315.0621.
.4.20. 1-Phenyl-4-[(Z)-1-(trimethylsilyl)hex-1-enyl]-1H-1,2,3-triazole (6aa). Yellow
4
15

ACCEPTED MANUSCRIPT
1
liquid, hexane-EtOAc (95:5) as eluent. H NMR (600 MHz, CDCl ): δ = 0.27 (s, 9H),
3
0
7
.93 (t, J = 6.8 Hz, 3H), 1.36-1.51 (m, 4H), 2.31-2.37 (m, 2H), 6.63 (t, J = 7.4 Hz, 1H),
1
3
.39-7.43 (m, 1H), 7.48-7.54 (m, 2H), 7.71 (s, 1H), 7.72-7.77 (m, 2H). C NMR (150
MHz, CDCl ): δ = 0.7 (Me Si), 13.9 (CH ), 22.3 (CH ), 31.7 (CH ), 31.8 (CH ), 117.1
3
3
3
2
2
2
(=CH), 120.0 (2 × CHarom), 128.2 (CHarom), 129.5 (2 × CHarom), 137.0 (Carom), 149.3
(
=CH), 152.4 (=C). IR (KBr): ν = 2954, 2925, 2856, 1514, 1247, 1222, 1045, 877, 839
ꢀ
1
+
cm . HRMS (ESI): m/z [M + Na] calcd for C H N NaSi: 322.1707; found 322.1706.
1
7
25
3
4
.4.21.
1-(4-Methoxyphenyl)-4-[(Z)-1-(trimethylsilyl)hex-1-enyl]-1H-1,2,3-triazole
1
(6ab). Yellow liquid, hexane-EtOAc (9:1) as eluent. H NMR (600 MHz, CDCl ): δ =
3
0
6
0
.27 (s, 9H), 0.93 (t, J = 6.8 Hz, 3H), 1.36-1.50 (m, 4H), 2.30-2.37 (m, 2H), 3.84 (s, 3H),
1
3
.62 (br s, 1H), 6.97-7.02 (m, 2H), 7.58-7.70 (m, 3H). C NMR (150 MHz, CDCl ): δ =
3
.9 (Me Si), 14.0 (CH ), 22.4 (CH ), 31.9 (2 × CH ), 55.5 (CH ), 114.6 (2 × CHarom),
3
3
2
2
3
117.5 (=CH), 121.8 (2 × CHarom), 129.8 (=C), 130.7 (Carom), 149.1 (=CH), 152.4 (=C),
1
59.5 (Carom). IR (KBr): ν = 2956, 2929, 2856, 1595, 1514, 1463, 1253, 1222, 1039, 987,
ꢀ
1
+
8
77, 833, 759 cm . HRMS (ESI): m/z [M + Na] calcd for C H ON NaSi: 352.1810;
18 27 3
found 352.1811.
4
.4.22. 1-(4-Methylphenyl)-4-[(Z)-1-(trimethylsilyl)hex-1-enyl]-1H-1,2,3-triazole (6ac).
1
Yellowish liquid, hexane-EtOAc (95:5) as eluent. H NMR (600 MHz, CDCl ): δ = 0.28
3
(
s, 9H), 0.93 (t, J = 6.8 Hz, 3H), 1.35-1.49 (m, 4H), 2.30-2.36 (m, 2H), 2.37 (s, 3H),
1
3
6
.61 (t, J = 7.6 Hz, 1H), 7.24-7.28 (m, 2H), 7.58-7.62 (m, 2H), 7.70 (s, 1H). C NMR
(
150 MHz, CDCl ): δ = 0.7 (Me Si), 13.8 (CH ), 20.8 (CH ), 22.2 (CH ), 31.7 (CH ),
3 3 3 3 2 2
3
1.7 (CH ), 117.0 (=CH), 119.8 (2 × CHarom), 129.6 (=C), 129.9 (2 × CHarom), 134.7
2
(
Carom), 138.0 (Carom), 148.9 (=CH), 152.3 (=C). IR (KBr): ν = 2954, 2925, 2856, 1515,
ꢀ
1
+
1
247, 1222, 1045, 1028, 987, 877, 839, 758 cm . HRMS (ESI): m/z [M + Na] calcd
for C H N NaSi: 336.1861; found 336.1862.
1
8
27
3
4
.4.23. 1-(2-Methylphenyl)-4-[(Z)-1-(trimethylsilyl)hex-1-enyl]-1H-1,2,3-triazole (6ad).
1
Yellowish liquid, hexane-EtOAc (95:5) as eluent. H NMR (600 MHz, CDCl ): δ = 0.27
3
(
s, 9H), 0.93 (t, J = 7.2 Hz, 3H), 1.36-1.51 (m, 4H), 2.23 (s, 3H), 2.32-2.37 (m, 2H),
1
3
6
.68 (t, J = 7.6 Hz, 1H), 7.29-7.41 (m, 4H), 7.46 (s, 1H). C NMR (150 MHz, CDCl ):
3
δ = 0.8 (Me Si), 14.0 (CH ), 17.9 (CH ), 22.5 (CH ), 31.9 (CH ), 31.9 (CH ), 120.9
3
3
3
2
2
2
(=CH), 125.9 (CHarom), 126.7 (CHarom), 129.4 (=C), 129.5 (CHarom), 131.3 (CHarom),
1
1
33.6 (Carom), 136.7 (Carom), 149.3 (=CH), 151.4 (=C). IR (KBr): ν = 2954, 2927, 2856,
ꢀ
1
+
500, 1463, 1247, 1043, 877, 840, 761 cm . HRMS (ESI): m/z [M + Na] calcd for
16

ACCEPTED MANUSCRIPT
C H N NaSi: 336.1861; found 336.1861.
18
27
3
4
.4.24. 1-(4-Fluorophenyl)-4-[(Z)-1-(trimethylsilyl)hex-1-enyl]-1H-1,2,3-triazole (6ae).
1
Yellowish liquid, hexane-EtOAc (9:1) as eluent. H NMR (600 MHz, CDCl ): δ = 0.27
3
(
s, 9H), 0.93 (t, J = 6.8 Hz, 3H), 1.35-1.49 (m, 4H), 2.30-2.36 (m, 2H), 6.61 (t, J = 7.6
1
3
Hz, 1H), 7.15-7.21 (m, 2H), 7.69-7.74 (m, 3H). C NMR (150 MHz, CDCl ): δ = 0.7
3
(
Me Si), 13.8 (CH ), 22.3 (CH ), 31.7 (2 × CH ), 116.4 (d, J = 23.1 Hz, 2 × CHarom),
3 3 2 2
1
1
1
3
17.2 (=CH), 122.0 (d, J = 8.7 Hz, 2 × CHarom), 129.5 (=C), 133.3 (Carom), 149.3 (=CH),
52.7 (=C), 161.9 (d, J = 248.5 Hz, Carom). IR (KBr): ν = 2956, 2927, 2856, 1514, 1245,
ꢀ
1
+
222, 1045, 877, 839 cm . HRMS (ESI): m/z [M + Na] calcd for C H N FNaSi:
1
7
24
3
40.1611; found 340.1612.
4
.4.25. 1-(3-Acetoxyphenyl)-4-[(Z)-1-(trimethylsilyl)hex-1-enyl]-1H-1,2,3-triazole (6af).
1
Yellowish liquid, hexane-EtOAc (8:2) as eluent. H NMR (600 MHz, CDCl ): δ = 0.29
3
(s, 9H), 0.93 (t, J = 6.8 Hz, 3H), 1.36-1.50 (m, 4H), 2.31-2.38 (m, 2H), 2.66 (s, 3H),
6
.62 (t, J = 7.5 Hz, 1H), 7.58-7.65 (m, 1H), 7.89 (s, 1H), 7.94-7.99 (m, 1H), 8.00-8.05
1
3
(m, 1H), 8.29 (s, 1H). C NMR (150 MHz, CDCl ): δ = 0.8 (Me Si), 14.0 (CH ), 22.4
3 3 3
(
CH ), 26.7 (CH ), 31.8 (CH ), 31.8 (CH ), 117.2 (=CH), 119.3 (CHarom), 124.3
3 2 2 2
(CHarom), 127.9 (CHarom), 129.6 (=C), 130.1 (CHarom), 137.5 (Carom), 138.3 (Carom), 149.6
(
=CH), 153.1 (=C), 196.7 (C=O). IR (KBr): ν = 2956, 2927, 2858, 1693, 1591, 1448,
ꢀ
1
+
1
357, 1259, 1224, 1045, 877, 840, 792, 686 cm . HRMS (ESI): m/z [M + Na] calcd
for C H ON NaSi: 364.1810; found 364.1811.
1
9
27
3
4
.4.26. 1-(3-Cyanophenyl)-4-[(Z)-1-(trimethylsilyl)hex-1-enyl]-1H-1,2,3-triazole (6ag).
1
White solid, hexane-EtOAc (9:1) as eluent, mp. 98-99 ºC. H NMR (600 MHz, CDCl ):
3
δ = 0.27 (s, 9H), 0.94 (t, J = 6.8 Hz, 3H), 1.35-1.51 (m, 4H), 2.31-2.38 (m, 2H), 6.62 (t,
1
3
J = 7.5 Hz, 1H), 7.63-7.72 (m, 2H), 7.75 (s, 1H), 8.03-8.08 (m, 2H). C NMR (150
MHz, CDCl ): δ = 0.8 (Me Si), 14.0 (CH ), 22.4 (CH ), 31.8 (CH ), 31.9 (CH ), 114.0
3
3
3
3
2
2
(CHarom), 116.8 (=CH), 117.5 (≡C), 123.1 (CHarom), 124.1 (CHarom), 129.4 (=C), 130.8
(
CHarom), 131.5 (CHarom), 137.7 (Carom), 150.1 (=CH), 153.4 (=C). IR (KBr): ν = 3149,
ꢀ
1
2
954, 2929, 2233, 1732, 1589, 1487, 1247, 1226, 1051, 1004, 883, 839, 758, 682 cm .
+
HRMS (ESI): m/z [M + Na] calcd for C H N NaSi: 347.1662; found 347.1661.
1
8
24
4
4
.4.27. 1-(3-Nitrophenyl)-4-[(Z)-1-(trimethylsilyl)hex-1-enyl]-1H-1,2,3-triazole (6ah).
1
Yellow solid, hexane-EtOAc (9:1) as eluent, mp. 100-101 ºC. H NMR (600 MHz,
CDCl ): δ = 0.28 (s, 9H), 0.94 (t, J = 6.8 Hz, 3H), 1.36-1.51 (m, 4H), 2.32-2.38 (m, 2H),
3
17

ACCEPTED MANUSCRIPT
6
.62 (t, J = 7.6 Hz, 1H), 7.72-7.76 (m, 1H), 7.84 (s, 1H), 8.19-8.23 (m, 1H), 8.25-8.29
1
3
(m, 1H), 8.57-8.59 (m, 1H). C NMR (150 MHz, CDCl ): δ = 0.8 (Me Si), 14.0 (CH ),
3 3 3
2
2.4 (CH ), 31.8 (CH ), 31.9 (CH ), 114.8 (CHarom), 116.9 (=CH), 122.7 (CHarom), 125.7
3 2 2
(CHarom), 129.4 (=C), 130.8 (CHarom), 137.9 (Carom), 148.9 (Carom), 150.1 (=CH), 153.6
(
=C). IR (KBr): ν = 3139, 3101, 2952, 2925, 2860, 1539, 1350, 1244, 1228, 1043, 879,
ꢀ
1
+
8
39, 808, 736, 669 cm . HRMS (ESI): m/z [M + Na] calcd for C H O N NaSi:
17 24 2 4
3
67.1560; found 367.1560.
4
.4.28. 1-Phenyl-4-[(Z)- 2-phenyl-1-(trimethylsilyl)ethenyl]-1H-1,2,3-triazole (6ba).
1
Off-white solid, hexane-EtOAc (9:1) as eluent, mp. 111-112 ºC. H NMR (600 MHz,
CDCl ): δ = 0.07 (s, 9H), 7.28-7.37 (m, 5H), 7.40-7.45 (m, 1H), 7.50-7.55 (m, 2H),
3
1
3
7
.76-7.80 (m, 2H), 7.84 (s, 1H), 7.90 (s, 1H). C NMR (150 MHz, CDCl ): δ = 0.7
3
(
Me Si), 117.5 (=CH), 120.3 (2 × CHarom), 127.4 (CHarom), 127.9 (2 × CHarom), 128.4
3
(CHarom), 128.5 (2 × CHarom), 129.7 (2 × CHarom), 133.8 (Carom), 137.1 (Carom), 139.4
(
=C), 146.1 (=CH), 152.4 (=C). IR (KBr): ν = 2952, 1598, 1500, 1417, 1247, 1224,
ꢀ
1
+
1
3
047, 1035, 840, 756, 690 cm . HRMS (ESI): m/z [M + Na] calcd for C H N NaSi:
19 21 3
42.1393; found 342.1394.
4
.4.29. 1-(4-Methoxyphenyl)-4-[(Z)-2-phenyl-1-(trimethylsilyl)ethenyl]-1H-1,2,3-
1
triazole (6bb). White solid, hexane-EtOAc (9:1) as eluent, mp. 100-102 ºC. H NMR
(
600 MHz, CDCl ): δ = 0.07 (s, 9H), 3.86 (s, 3H), 7.00-7.04 (m, 2H), 7.28-7.37 (m, 5H),
3
1
3
7
.65-7.69 (m, 2H), 7.81 (s, 1H), 7.83 (s, 1H). C NMR (150 MHz, CDCl ): δ = 0.8
3
(
Me Si), 55.6 (CH ), 114.7 (2 × CHarom), 117.7 (=CH), 121.9 (2 × CHarom), 127.4
3 3
(CHarom), 127.9 (2 × CHarom), 128.5 (2 × CHarom), 130.6 (Carom), 133.9 (Carom), 139.5
(
=C), 145.9 (=CH), 152.2 (=C), 159.6 (Carom). IR (KBr): ν = 2956, 1515, 1255, 1226,
ꢀ
1
+
1
043, 839, 754, 698 cm . HRMS (ESI): m/z [M + Na] calcd for C H ON NaSi:
20 20 3
3
69.1264; found 369.1265.
4
.4.30. 1-(4-Methylphenyl)-4-[(Z)-2-phenyl-1-(trimethylsilyl)ethenyl]-1H-1,2,3-
1
triazole (6bc). White solid, hexane-EtOAc (9:1) as eluent, mp. 112-113 ºC. H NMR
(
600 MHz, CDCl ): δ = 0.07 (s, 9H), 2.46 (s, 3H), 7.27-7.37 (m, 7H), 7.62-7.67 (m,
3
13
2
H), 7.81-7.87 (m, 2H). C NMR (150 MHz, CDCl ): δ = 0.8 (Me Si), 21.1 (CH ),
3 3 3
117.5 (=CH), 120.2 (2 × CHarom), 127.4 (CHarom), 127.9 (2 × CHarom), 128.5 (2 ×
CHarom), 130.2 (2 × CHarom), 133.9 (Carom), 134.9 (Carom), 138.5 (Carom), 139.5 (=C),
1
7
45.9 (=CH), 152.3 (=C). IR (KBr): ν = 2954, 1519, 1247, 1224, 1031, 989, 840, 817,
ꢀ
1
+
54, 698, 667 cm . HRMS (ESI): m/z [M + Na] calcd for C H N NaSi: 353.1315;
2
0
20
3
18

ACCEPTED MANUSCRIPT
found 353.1316.
4
.4.31. 1-(2-Methylphenyl)-4-[(Z)-2-phenyl-1-(trimethylsilyl)ethenyl]-1H-1,2,3-triazole
1
(
6bd). Yellowish liquid, hexane-EtOAc (95:5) as eluent. H NMR (600 MHz, CDCl ):
3
1
3
δ = 0.07 (s, 9H), 2.24 (s, 3H), 7.25-7.41 (m, 9H), 7.65 (s, 1H), 7.89 (s, 1H). C NMR
(150 MHz, CDCl ): δ = 0.6 (Me Si), 17.7 (CH ), 121.1 (=CH), 125.7 (CHarom), 126.6
3 3 3
(CHarom), 127.3 (CHarom), 127.7 (2 × CHarom), 128.3 (2 × CHarom), 129.5 (CHarom),
1
1
31.2 (CHarom), 133.5 (Carom), 133.5 (Carom), 136.4 (Carom), 139.3 (=C), 145.8 (=CH),
ꢀ
1
51.1 (=C). IR (KBr): ν = 2952, 1498, 1247, 1045, 840, 761, 698 cm . HRMS (ESI):
+
m/z [M + Na] calcd for C H N NaSi: 353.1315; found 353.1314.
20
20
3
4
.4.32. 1-(4-Fluorophenyl)-4-[(Z)-2-phenyl-1-(trimethylsilyl)ethenyl]-1H-1,2,3-triazole
1
(6be). White solid, hexane-EtOAc (9:1) as eluent, mp. 123-124 ºC. H NMR (600 MHz,
CDCl ): δ = 0.07 (s, 9H), 7.18-7.24 (m, 2H), 7.28-7.37 (m, 5H), 7.72-7.77 (m, 2H), 7.82
3
1
3
(
s, 1H), 7.86 (s, 1H). C NMR (150 MHz, CDCl ): δ = 0.7 (Me Si), 116.6 (d, J = 23.1
3 3
Hz, 2 × CHarom), 117.6 (=CH), 122.2 (d, J = 8.6 Hz, 2 × CHarom), 127.5 (CHarom), 127.9
2 × CHarom), 128.5 (2 × CHarom), 133.4 (Carom), 133.7 (Carom), 139.3 (=C), 146.2 (=CH),
(
1
7
3
52.6 (=C), 162.2 (d, J = 248.5 Hz, Carom). IR (KBr): ν = 3112, 1514, 1228, 1053, 835,
ꢀ
1
+
61 cm . HRMS (ESI): m/z [M + Na] calcd for C H N FNaSi: 360.1299; found
1
9
20
3
60.1300.
4
.4.33. 1-(3-Acetoxyphenyl)-4-[(Z)-2-phenyl-1-(trimethylsilyl)ethenyl]-1H-1,2,3-triazole
1
(6bf). White solid, hexane-EtOAc (8:2) as eluent, mp. 112-113 ºC. H NMR (600 MHz,
CDCl ): δ = 0.08 (s, 9H), 2.69 (s, 3H), 7.29-7.38 (m, 5H), 7.66 (t, J = 7.6 Hz, 1H), 7.83
3
1
3
(
s, 1H), 7.99 (s, 1H), 7.99-8.03 (m, 1H), 8.06-8.09 (m, 1H), 8.32 (br s, 1H). C NMR
(
150 MHz, CDCl ): δ = 0.7 (Me Si), 26.7 (CH ), 117.3 (=CH), 119.3 (CHarom), 124.5
3
3
3
(
CHarom), 127.5 (CHarom), 127.9 (2 × CHarom), 128.1 (CHarom), 128.5 (2 × CHarom), 130.1
CHarom), 133.7 (Carom), 137.5 (Carom), 138.4 (Carom), 139.3 (=C), 146.3 (=CH), 152.9
=C), 196.7 (C=O). IR (KBr): ν = 2954, 1693, 1591, 1488, 1448, 1357, 1259, 1226,
(
(
ꢀ
1
+
1
3
047, 842, 792, 756, 698 cm . HRMS (ESI): m/z [M + Na] calcd for C H ON NaSi:
21 23 3
84.1498; found 384.1499.
4
.4.34. 1-(3-Cyanophenyl)-4-[(Z)-2-phenyl-1-(trimethylsilyl)ethenyl]-1H-1,2,3-triazole
1
(6bg). White solid, hexane-EtOAc (9:1) as eluent, mp. 182-184 ºC. H NMR (600 MHz,
CDCl ): δ = 0.07 (s, 9H), 7.29-7.39 (m, 5H), 7.66-7.74 (m, 2H), 7.82 (s, 1H), 7.94 (s,
3
1
3
1
H), 8.07-8.12 (m, 2H). C NMR (150 MHz, CDCl ): δ = 0.7 (Me Si), 114.1 (Carom),
3 3
19

ACCEPTED MANUSCRIPT
117.0 (=CH), 117.5 (≡C), 123.3 (CHarom), 124.2 (CHarom), 127.6 (CHarom), 127.9 (2 ×
CHarom), 128.5 (2 × CHarom), 130.8 (CHarom), 131.7 (CHarom), 133.5 (Carom), 137.6 (Carom),
1
39.1 (=C), 146.7 (=CH), 153.3 (=C). IR (KBr): ν = 3138, 2235, 1589, 1498, 1444,
ꢀ
1
+
1
245, 1228, 1047, 842, 802, 754, 696, 677 cm . HRMS (ESI): m/z [M + Na] calcd for
C H N NaSi: 367.1350; found 367.1349.
20
20
4
4
.4.35. 1-(3-Nitrophenyl)-4-[(Z)-2-phenyl-1-(trimethylsilyl)ethenyl]-1H-1,2,3-triazole
1
(6bh). Light-brown solid, hexane-EtOAc (8:2) as eluent, mp. 200 ºC (dec). H NMR
(
600 MHz, CDCl ): δ = 0.08 (s, 9H), 7.30-7.39 (m, 5H), 7.74-7.79 (m, 1H), 7.83 (s,
3
1
3
1
H), 8.01 (s, 1H), 8.22-8.27 (m, 1H), 8.29-8.34 (m, 1H), 8.61-8.64 (m, 1H). C NMR
(
150 MHz, CDCl ): δ = 0.7 (Me Si), 114.9 (CHarom), 117.1 (=CH), 122.8 (CHarom),
3 3
1
25.7 (CHarom), 127.7 (CHarom), 127.9 (2 × CHarom), 128.5 (2 × CHarom), 130.9 (CHarom),
33.5 (Carom), 137.8 (Carom), 139.1 (Carom), 146.8 (=CH), 148.9 (Carom), 153.4 (=C). IR
1
(
KBr): ν = 3138, 1535, 1488, 1350, 1245, 1226, 1043, 889, 844, 806, 756, 734, 711,
ꢀ
1
+
6
96 cm . HRMS (ESI): m/z [M + Na] calcd for C H O N NaSi: 387.1248; found
19 20 2 4
3
87.1247.
Supplementary data
Supplementary data associated with this article can be found in the online version,
at
References and notes
1
2
(a) Tornøe, C. W.; Christensen C.; Meldal, M. J. Org. Chem. 2002, 67, 3057; (b)
Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem. Int. Ed.
2002, 41, 2596.
For selected reviews, see: (a) Bock, ꢁ. D.; Hiemstra, H.; Van Maarseveen, J. H. Eur.
J. Org. Chem. 2006, 51; (b) Meldal, M.; Tornøe, C. W. Chem. Rev. 2008, 108, 2952;
(c) Kappe, C. O.; Van der Eycken, E. Chem, Soc. Rev. 2010, 39, 1280; (d) Hein, J. E.;
Fokin, V. V. Chem. Soc. Rev. 2010, 39, 1302; (e) Díez-González, S. Catal. Sci.
Technol. 2011, 1, 166; (f) Totobenazara, J.; Burke, A. J. Tetrahedron Lett. 2015, 56,
2
853.
For recent reviews, see: (a) Agalave, S. G.; Maujan, S. R.; Pore, V. S. Chem. Asian J.
011, 6, 2696; (b) Haider, S.; Alam, M. S.; Hamid, H. Inflamm. Cell Signal. 2014, 1,
e95.
3
2
20

ACCEPTED MANUSCRIPT
4
For recent reviews, see: (a) Moses, J. E.; Moorhouse, A. D. Chem. Soc. Rev. 2007,
36, 1249; (b) Dedola, S.; Nepogodiev, S. A.; Field, R. A. Org. Biomol. Chem. 2007, 5,
1006; (c) Gramlich, P. M. E.; Wirges, C. T.; Manetto, A.; Carell, T. Angew. Chem. Int.
Ed. 2008, 47, 8350; (d) Amblard, F.; Cho, J. H.; Schinazi, R. F. Chem. Rev. 2009, 109,
207; (e) Best, M. D. Biochemistry 2009, 48, 6571; (f) Mamidyala, S. K.; Finn, M. G.
Chem. Soc. Rev. 2010, 39, 1252; (g) Holub, J. M.; Kirshenbaum, K. Chem. Soc. Rev.
010, 39, 1325; (h) El-Sagheer, A. H.; Brown, T. Chem. Soc. Rev. 2010, 39, 1388; (i)
4
2
Aragão-Leoneti, V.; Campo, V. L.; Gomes, A. S.; Field, R. A.; Carvalho, I.
Tetrahedron 2010, 66, 9475; (j) Pedersen, D. S.; Abell, A. Eur. J. Org. Chem. 2011,
2
399; (k) Altintas, O.; Tunca, U. Chem. Asian J. 2011, 6, 2584; (l) Li, X. Chem. Asian
J. 2011, 6, 2606; (m) Thirumurugan, P.; Matosiuk, D.; Jozwiak, K. Chem. Rev. 2013,
13, 4905; (n) Lauria, A.; Delisi, R.; Mingoia, F.; Terenzi, A.; Martorana, A.; Barone
1
G.; Almerico, A. M. Eur. J. Org. Chem. 2014, 3289.
5
For recent reviews, see: (a) Lutz, J.-F. Angew. Chem. Int. Ed. 2007, 46, 1018; (b)
Meldal, M. Macromol. Rapid Commun. 2008, 29, 1016; (c) Iha, R. K.; Wooley, K.
L.; Nyström, A. M.; Burke, D. J.; Kade, M. J.; Hawker, C. T. Chem. Rev. 2009, 109,
5
620; (d) Droumaguet, C. L.; Wang, C.; Wang, Q. Chem. Soc. Rev. 2010, 39, 1233;
(e) Hänni, K. D.; Leigh, D. A. Chem. Soc. Rev. 2010, 39, 1240; (f) Golas, P. L.;
Matyjaszewski, K. Chem. Soc. Rev. 2010, 39, 1338; (g) Lau, Y. H.; Rutledge, P. J.;
Watkinson, M.; Todd, M. H. Chem. Soc. Rev. 2011, 40, 2848; (h) Li, Y.; Cai, C.
Chem. Asian J. 2011, 6, 2592; (i) Yigit, S.; Sanyal, R.; Sanyal, A. Chem. Asian J.
2
011, 6, 2648; (j) Kempe, K.; Krieg, A.; Becer, C. R.; Schubert, U. S. Chem. Soc.
Rev. 2012, 41, 176; (k) Astruc, D.; Liang, L.; Rapakousiou, A.; Ruiz, J. Acc. Chem.
Res. 2012, 45, 630; (l) Xi, W.; Scott, T. F.; Kloxin, C. J.; Bowman, C. N. Adv. Funct.
Mater. 2014, 24, 2572.
6
For examples, see: (a) Krasiński, A.; Fokin, V. V.; Sharpless, K. B. Org. Lett. 2004, 6,
1
237; (b) Zhang, L.; Chen, X.; Xue, P.; Sun, H. H. Y.; Williams, I. D.; Sharpless, K.
B.; Fokin, V. V.; Jia, G. J. Am. Chem. Soc. 2005, 127, 15998; (c) Rasmussen, L. K.;
Boren, B. C.; Fokin, V. V. Org. Lett. 2007, 9, 5337; (d) Boren, B. C.; Narayan, S.;
Rasmussen, L. K.; Zhang, L.; Zhao, H.; Lin, Z.; Jia, G.; Fokin, V. V. J. Am. Chem.
Soc. 2008, 130, 8923; (e) Kwok, S. W.; Fotsing, J. R.; Fraser, R. J.; Rodionov, V. O.;
Fokin, V. V. Org. Lett. 2010, 12, 4217; (f) Johansson, J. R.; Lincoln, P.; Nordén, B.;
Kann, N. J. Org. Chem. 2011, 76, 2355; (g) Koguchi, S.; Izawa, K. Synthesis 2012,
4
4, 3603; (h) Smith, C. D.; Greaney, M. F. Org. Lett. 2013, 15, 4826; (i) Hong, L.;
Lin, W.; Zhang, F.; Liu, R.; Zhou, X. Chem. Commun. 2013, 49, 5589; (j) Koguchi,
S.; Izawa, K. ACS Comb. Sci. 2014, 16, 381.
21

ACCEPTED MANUSCRIPT
7
(a) Feldman, A. K.; Colasson, B.; Fokin, V. V. Org. Lett. 2004, 6, 3897; (b) Andersen,
J.; Bolvig, S.; Liang, X. Synlett 2005, 2941; (c) Zhao, Y.-B.; Yan, Z.-Y.; Liang, Y.-M.
Tetrahedron Lett. 2006, 47, 1545; (d) Miao, T.; Wang, L. Synthesis 2008, 363. (e)
Ackermann, L.; Potukuchi, H. K.; Landsberg, D.; Vicente, R. Org. Lett. 2008, 10,
3
081; (f) Dururgkar, K. A.; Gonnade, R. G.; Ramana, C. V. Tetrahedron 2009, 65,
974; (g) Yan, J.; Wang, L. Synthesis 2010, 447; (h) Kolarovič, A.; Schnürch, M.;
3
Mihovilovic, M. D. J. Org. Chem. 2011, 76, 2613.
8
9
(a) Tao, C.-Z.; Cui, X.; Li, J.; Liu, A.-X.; Liu, L.; Guo, Q.-X. Tetrahedron Lett. 2007,
4
8, 3525; (b) Grimes, K. D.; Gupte, A.; Aldrich, C. C. Synthesis 2010, 1441; (c)
Mohammed, S.; Padala, A. K.; Dar, B. A.; Singh, B.; Sreedhar, B.; Vishwakarma, R.
A.; Bharate, S. B. Tetrahedron 2012, 68, 8156; (d) Kumar, B. S. P. A.; Reddy, K. H.
V.; Karnakar, K.; Satish, G.; Nageswar, Y. V. D. Tetrahedron Lett. 2015, 56, 1968.
(a) Barral, K.; Moorhouse, A. D.; Moses, J. E. Org. Lett. 2007, 9, 1809; (b) Smith, N.
M.; Greaves, M. J.; Jewell, R.; Perry, M. W. D.; Stocks, M. J.; Stonehouse, J. P.
Synlett 2009, 1391; (c) Kumar, D.; Reddy, V. B. Synthesis 2010, 1687; (d) Fletcher, J.
T.; Reilly, J. E. Tetrahedron Lett. 2011, 52, 5512; (e) Zarei, A.; Khazdooz, L.;
Hajipour, A. R.; Aghaei, H.; Azizi, G. Synthesis 2012, 44, 3353.
1
0 (a) Xu, M.; Kuang, C.; Wang, Z.; Yang, Q.; Jiang, Y. Synthesis 2011, 223; (b)
Kavitha, M.; Mahipal, B.; Mainkar, P. S.; Chandrasekhar, S. Tetrahedron Lett. 2011,
5
2, 1658.
1 (a) Díez-González, S.; Correa, A.; Cavallo, L.; Nolan, S. P. Chem. Eur. J. 2006, 12,
558; (b) Thibault, R. J.; Takizawa, K.; Lowenheilm, P.; Helms, B.; Mynar, J. L.;
1
7
Fréchet, J. M. J.; Hawker, C. J. J. Am. Chem. Soc. 2006, 128, 12084; (c) Hu, M.; Li,
J.; Yao, S. Q. Org. Lett. 2008, 10, 5529; (d) Alonso, F.; Moglie, Y.; Radivoy, G.; Yus,
M. Tetrahedron Lett. 2009, 50, 2358; (e) Shao, C.; Zhu, R.; Luo, S.; Zhang, Q.;
Wang, X.; Hu, Y. Tetrahedron Lett. 2011, 52, 3782; (f) Liu, P. N.; Siyang, H. X.; Tse,
S. K. S.; Jia, G. J. Org. Chem. 2012, 77, 5844.
1
2 Hoshi, M.; Okimoto, M.; Oikawa, A.; Miyawaki, S.; Shimotori, Y. RSC Adv. 2014, 4,
2
124.
1
3 (a) Hoshi, M.; Nakayabu, H.; Shirakawa, K. Synthesis 2005, 1991; (b) Hoshi, M.;
Suzuki, S.; Saitoh, S.; Okimoto, M.; Shirakawa, K. Tetrahedron Lett. 2007, 48, 119;
(c) Hoshi, M.; Iizawa, T.; Okimoto, M.; Shirakawa, K. Synthesis 2008, 3591; (d)
Hoshi, M.; Yamazaki, H.; Okimoto, M. Synlett 2010, 2461; (e) Hoshi, M.; Okimoto,
M.; Nakamura, S.; Takahashi, S. Synthesis 2011, 3839.
1
1
4 Compound 2a was isolated in 70% yield based on Me SiC≡CBr used.
3
5 Hoshi, M.; Kawamura, N.; Shirakawa, K. Synthesis 2006, 1961.
22

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1
6 (a) Aucagne, V.; Leigh, D. A. Org. Lett. 2006, 8, 4505; (b) Fletcher, J. T.; Bumgarner,
B. J.; Engels, N. D.; Skoglund, D. A. Organometallics 2008, 27, 5430; (c) Lőrincz,
K.; Kele, P.; Novák, Z. Synthesis 2009, 3527; (d) Fiandanese, V.; Bottalico, D.;
Marchese, G.; Punzi, A.; Quarta, M. R.; Fittipaldi, M. Synthesis 2009, 3853; (e)
Friscourt, F.; Boons, G.-J. Org. Lett. 2010, 12, 4936; (f) Ladouceur, S.; Soliman, A.
M.; Zysman-Colman, E. Synthesis 2011, 3604; (g) Hwang, S.; Bae, H.; Kim, S.; Kim,
S. Tetrahedron 2012, 68, 1460; (h) Wu, L.; Chen, Y.; Tang, M.; Song, X.; Chen, G.;
Song, X.; Lin, Q. Synlett 2012, 23, 1529; (i) Stefani, H. A.; Leal, D. M.; Manarin, F.
Tetrahedron Lett. 2012, 53, 6495.
1
1
7 Utimoto, K.; Kitai, M.; Nozaki, H. Tetrahedron Lett., 1975, 2825.
1
8 The H NMR spectrum of 1-phenyl-4-[(E)-hex-1-enyl]-1H-1,2,3-triazole exhibits the
alkenyl protons at δ = 6.46 (d, J = 15.8 Hz, 1H) and 5.52 (dt, J = 15.8 and 6.8 Hz,
1
H) ppm.
9 Hofmeister, H.; Annen, K.; Laurent, H.; Wiechert, R. Angew. Chem., In. Ed. Engl.
984, 23, 727.
0 Brown, H. C.; Mandal, A. K.; Kulkarni, S. U. J. Org. Chem. 1977, 42, 1392.
1
2
1
23