Cross-coupling reaction of iodo-1,2,3-triazoles catalyzed by palladium

Article abstract of DOI:10.1055/s-2005-872119

The Suzuki, Heck and Sonogashira reactions of 1,4-di-substituted 5-iodo-1,2,3-trizaoles were studied. A versatile method for regioselective synthesis of 1,4,5-trisubstituted-1,2,3-triazoles was developed. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2005-872119

2730
PAPER
Cross-Coupling Reaction of Iodo-1,2,3-triazoles Catalyzed by Palladium
C
ross-Cou
u
pling Reacti
a
on of Iodo-
n
1, 2,3-triazoles Deng, Yong-Ming Wu,* Qing-Yun Chen*
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Rd,
Shanghai 200032, P. R. China
Fax +86(21)64166128; E-mail: ymwu@mail.sioc.ac.cn
Received 12 April 2005; revised 10 May 2005
cases. Recently, Sharpless reported a method of regiose-
Abstract: The Suzuki, Heck and Sonogashira reactions of 1,4-di-
lective synthesis of 1,2,3-triazoles using Cu(I) salt as ca-
substituted 5-iodo-1,2,3-trizaoles were studied. A versatile method
talysis,18 providing a convenient method for synthesis of
for regioselective synthesis of 1,4,5-trisubstituted-1,2,3-triazoles
1,4-disbustituted 1,2,3-triazole under mild conditions. We
recently reported a one-pot method for regioselective syn-
thesis of fluoroalkylated 1,4-disubstituted 5-iodo-1,2,3-
trizaoles catalyzed by this similar methodology.19 Herein
we would like to report the cross coupling reaction of
iodo-1,2,3-triazoles.
was developed.
Key Words: Suzuki reaction, Heck reaction, Sonogashira reaction,
palladium, 1,2,3-trizaoles
Transition metal-catalyzed cross coupling reactions are
powerful C–C bond formation methods in organic chem-
istry, especially between C(sp2) centers at which typical
SN substitutions cannot operate.1 Among them, palladi-
um(0) catalysts are the most important one. During the
past two decades, palladium catalysts have emerged as ex-
tremely powerful tools for the construction of carbon–car-
bon, as well as carbon–heteroatom bonds.2 Their
popularity stems in part from their tolerance of many
functional groups such as carbonyl and hydroxy groups,
which allows them to be employed in the synthesis of
highly complex molecules3 and industrial chemical pro-
cess.4 Recently this reaction has been expanded to het-
eroaromatics such as: pyridines,5 oxazoles,6 thiazoles,6,7
thiophenes,8 benzothiophenes,9 pyrazines,10 furans,11 py-
rimidines,12 and triazines.12 However, to the best of our
knowledge, there is no report related to the cross-coupling
reaction of triazoles, which may be due to the problems
associated with the synthesis of halotriazoles.
Suzuki Coupling Reaction
Among palladium-catalyzed cross-coupling processes,
the Suzuki coupling reaction of aryl and vinyl halides/tri-
flates with boronic acid is emerging as a favorite.20 It has
the following advantages: 1) commercial availability of a
large number of organoboranes especially boronic acids
and their esters; 2) stability of boronic acids towards heat,
air and moisture; 3) tolerance to a broad range of function-
al groups; 4) mild reaction conditions; 5) low toxicity; and
6) easy separation of inorganic boron from the reaction
mixture. Referring to the general Suzuki reaction condi-
tions, we performed the coupling of phenylboronic acid
with
4-butyl-5-iodo-1-(2,2,2-trifluoroethyl)-1H-1,2,3-
triazole19b as a model reaction. After testing various kinds
of bases, it was found that with Et3N, the result was very
complex and with K3PO4⋅3H2O, the reaction proceeded
very slow (72 h, 76% yield). If KOH was used as the base,
the reaction was complete after 10 hours, and the coupling
product was obtained in 97% yield. Thus cross-coupling
reactions were conducted under the optimum conditions
of PdCl2 (PPh3)2 as catalyst, KOH as base and THF as sol-
vent, and the results are shown in Table 1.
1,2,3-Triazoles have found wide use in pharmaceuticals,
agrochemicals, dyes, photographic materials and corro-
sion inhibition, etc.13 For example, there are numerous ex-
amples in the literature including anti-HIV activity,14
antimicrobial activity against Gram positive bacteria,15
selective b3 adrenergic receptor agonism by means of tri-
azole compounds.16 Because of their potential usefulness,
several synthetic methods have been developed for the
construction of triazole frameworks. Among them, the
most important and useful method is the 1,3-dipolar cy-
cloaddition of azide with alkyne.17 Two problems are,
however, encountered in this transformation: (1) reactivi-
ty of the substrates, either alkynes or azides should be ac-
tivated by an electron-withdrawing group, otherwise, the
reaction must be carried out at higher temperature; (2) the
regioselectivity of the products, for unsymmetrical
alkynes, a mixture of regioisomers is obtained in most
As shown in Table 1, when arylboronic acids are used as
substrates, the substituents on benzene ring have no effect
on the reaction, both electron-withdrawing (Table 1, en-
tries 6, 7) and electron-donating groups (Table 1, entries
8–10) give good to excellent yields, however, electron-
donating group on the benzene ring produces much better
yields (entry 10 vs. entry 7; entry 4 vs. entry 6). Further-
more, this reaction system was found to be compatible
with alkenylboronic acids (Table 1, entries 12–14), and
the conformation of the double bond was retained (3l:
JH,H = 16 Hz; 3m: JH,H = 16 Hz; 3n: JH,H = 16 Hz). When
R2 in 1 is an ester group, no reaction occurs under similar
condition.
SYNTHESIS 2005, No. 16, pp 2730–2738
Advanced online publication: 04.08.2005
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DOI: 10.1055/s-2005-872119; Art ID: F06905SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Cross-Coupling Reaction of Iodo-1,2,3-triazoles
2731
Table 1 Results of the Suzuki Reaction of 1,4-Disubstituted 5-Iodo-1,2,3-triazolesa
N
N
R1
N
N
R1
N
I
N
R3 B(OH)2
R3 R2
R2
3
1
2
Entry
1,4-Disubstituted 5-Iodo-1,2,3-triazole 1
Organoboronic Acid 2
Product 3
Yield (%)b
R1
R2
1
2
CF3CH2
C4H9
C4H9
Ph
PhB(OH)2
3a
3b
3c
3d
3e
3f
95
97
84
98
92
64
83
89
91
98
71
59
HCF2CF2CH2
HCF2CF2CH2
PhCH2
PhB(OH)2
3
PhB(OH)2
4
Ph
PhB(OH)2
5
C8H17
Ph
PhB(OH)2
6c
7
HCF2CF2CH2
PhCH2
Ph
4-CF3C6H4B(OH)2
4-CF3C6H4B(OH)2
4-MeOC6H4B(OH)2
4-MeOC6H4B(OH)2
4-MeOC6H4B(OH)2
4-CIC6H4B(OH)2
Ph
3g
3h
3i
8
CF3CH2
C4H9
C4H9
Ph
9
HCF2CF2CH2
PhCH2
10
11c
12
3j
PhCH2
Ph
3k
3l
HCF2CF2CH2
Ph
C5H11
B(OH)2
13
14
PhCH2
PhCH2
Ph
Ph
3m
3n
95
80
C5H11
B(OH)2
PhCH2OCH2
B(OH)2
a Reaction conditions: 1,4-disubstituted 5-iodo-1,2,3-triazole 1 (0.20 mmol), alkenylboronic acid 2 (0.30 mmol), PdCl2(PPh3)2 (4 mol%), KOH
(0.40 mmol), THF (3 mL), reflux.
b Isolated yield based on 1.
c Reaction conditions: 1,4-disubstituted 5-iodo-1,2,3-triazole 1 (0.20 mmol), alkenylboronic acid 2 (0.30 mmol), PdCl2(PPh3)2 (4 mol%),
K2CO3 (0.40 mmol), THF (3 mL), reflux.
and the results were satisfactory (Table 2, entry 3). The
conformation of the double bond in product 5a deter-
Heck Reaction
Heck reaction21 is certainly the most useful and versatile mined by 1H NMR was shown to be totally in the E-form
method of carbon–carbon bond formation involving sp2 (JH,H = 16 Hz), no Z-form stereoisomer could be detected.
carbon, which is impossible or difficult to achieve by tra- The results of Heck reaction of 1,4-disubstituted 5-iodo-
ditional means. The coupling of 5-iodo-4-phenyl-1- 1,2,3-triazoles 1 are shown in Table 3.
(2,2,3,3-tetrafluoropropyl)-1H-1,2,3-triazole and methyl
acrylate (4a) was first carried out as a model reaction in
As show in Table 3, 1,4-disubstituted 5-iodo-1,2,3-triaz-
oles 1 could undergo Heck reaction with some electron-
order to optimize the reaction conditions (Table 2). When
deficient terminal alkene smoothly. In most cases, confor-
we used the general Heck reaction conditions (Table 2,
mation of the double bond of the products was in E-form
(Table 3, entries 1–6,9,10) or E-isomer was in major
amount (Table 3, entries 7,8). It was found that when but-
entries 1,2), it was found that the conversion was very low
(about 30%). Adding silver salt22 to the reaction mixture
did not improve the situation. Jeffery had reported23 that
3-en-2-one was used as the substrate, the reaction was
with the use of Bu4NCl as the phase-transfer agent, DMF
completed in 4 hours and the conversion was up to 100%,
as solvent and NaHCO3 as base, Heck reactions can suc-
while for substrate, such as methyl acrylate, the reaction
cessfully proceed at or near room temperature. So we tried
should be prolonged to 24 hours. This might be due to the
the reaction under Jeffery’s conditions, using TBAB (tet-
electron-deficiency of double bond. When cyclohex-2-
rabutylammonium bromide) as the phase-transfer agent
Synthesis 2005, No. 16, 2730–2738 © Thieme Stuttgart · New York

2732
J. Deng et al.
PAPER
Table 2 Optimization of Heck Reaction of 1,4-Disubstituted 5-Iodo-1,2,3-triazoles 1a with Alkene 4a
N
N
HCF2CF2CH2
N
I
N
HCF2CF2CH2
H3COOC
N
N
COOCH3
Ph
Ph
5a
4a
1a
Entry
Conditions
Yielda (Conversion) (%)
97 (30)
1
2
3
Pd(OAc)2, PPh3, K2CO3, THF, reflux, 30 h
Pd(PPh3)2Cl2, K2CO3, THF, reflux, 30 h
Pd(OAc)2, NaHCO3, TBAB, DMF, 60 °C, 30 h
99 (31)
91 (71)
a Isolated yield based on consumed 1a.
Table 3 Results of the Heck Reaction of 1,4-Disubstituted 5-Iodo-1,2,3-triazoles 1a
N
N
R1
N
N
R1
N
I
N
R4
R2
R2
R4
1
4
5
Entry
1,4-Disubstituted 5-Iodo-1,2,3-triazole 1
Terminal Alkene 4
Product 5
Yield (%)b (Conversion, %)
R1
R2
Ph
Ph
Ph
1
2
3
HCF2CF2CH2
PhCH2
(E)-5a
(E)-5b
(E)-5c
92 (71)
98 (57)
88 (100)
COOCH3
COOCH3
CH3
HCF2CF2CH2
O
4
5
6
7
8
PhCH2
Ph
(E)-5d
(E)-5e
(E)-5f
99 (100)
87 (100)
88 (100)
70 (100)
85 (100)
CH3
O
HCF2CF2CH2
PhCH2
C4H9
C4H9
Ph
CH3
O
CH3
O
HCF2CF2CH2
PhCH2
(Z)-5g:(E)-5g¢
(Z:E = 24:76)
CN
Ph
(Z)-3h:(E)-3h¢
(Z:E = 30:70)
CN
9
PhCH2
PhCH2
Ph
Ph
(E)-5i
(E)-5j
62 (61)
92 (60)
CHO
Ph
10
a Reaction conditions: 1,4-disubstituted 5-iodo-1,2,3-triazole 1 (0.20 mmol), terminal alkene 4 (0.50 mmol), Pd(OAc)2 (10 mol%), TBAB (0.08
mmol), NaHCO3 (0.50 mmol), DMF (3 mL), 80 °C.
b Isolated yield based on consumed 1.
enone was used as substrate, the reaction did not occur at
all, due to the hindrance of the C–C double bond. As in the
Sonogashira Reaction
Suzuki reaction, when R2 in 1 was ester group, the reac- Direct introduction of sp2 carbon to alkynes by aryl ha-
tion did not occur either.
lides and alkynes catalyzed by Pd(0)-CuI is called the So-
nogashira coupling reaction,24 which is used extensively
for the preparation of arylalkynes or enynes. As in the
study of Suzuki and Heck reaction, we used phenylacet-
ylene and 5-iodo-4-phenyl-1-(2,2,2-trifluoroethyl)-1H-
Synthesis 2005, No. 16, 2730–2738 © Thieme Stuttgart · New York

PAPER
Cross-Coupling Reaction of Iodo-1,2,3-triazoles
2733
reported in parts per million relative to TMS as an external standard
1,2,3-triazole as model reaction. During optimizing the re-
action conditions, it was found that if DMF or THF was
used as the solvent, and Et3N or Et2NH was used as base,
the conversion was too low; besides the coupling product,
dehydrofluorinated product was also obtained. When
Ag2CO3 was used as base, the reaction conversion reached
to 56%, and the yield was 82%. Using K2CO3 as base, the
reaction was complete after four hours, and the desired
product was obtained in 98% yield. The coupling reac-
tions of various 1,4-disubstituted 5-iodo-1,2,3-triazoles 1
with terminal acetylene 6 were conducted under the opti-
mized conditions with PdCl2 (PPh3)2 as catalyst, K2CO3 as
base and THF as solvent, and the results are listed in
Table 4.
1
(TMS = 0) for H NMR spectra and CFCl3 as an internal standard
[(CFCl3) = 0] for 19F NMR (upfield shift being designated as nega-
tive) spectra. Coupling constants are given in Hertz (Hz). Low- and
high- resolution mass spectra were recorded on a Hewlett-Packard
HP-5989A and a Finnigan MAT spectrometer, respectively. Ele-
mental analyses were performed at this institute.
Suzuki Reaction of 1,4-Disubstituted 5-Iodo-1,2,3-triazoles 1;
General Procedure
Under N2, to a Schlenk tube, 1,2,3-triazole 1 (0.20 mmol), boronic
acid 2 (0.30 mmol), PdCl2(PPh3)2 (0.008 mmol, 4%), KOH (or
KCO3, 0.40 mmol), THF (3 mL) were added successively. The mix-
ture was stirred at 70 °C for 4–5 h. After removal of solvent, the
crude product was purified by flash chromatography on a silicon gel
column with hexane–EtOAc (5:1) as eluent.
4-Butyl-5-phenyl-1-(2,2,2-trifluoroethyl)-1H-1,2,3-triazole (3a)
White solid; mp 47–48 °C.
IR (KBr): 700, 1089, 1165, 1267, 2959 cm–1.
Conclusion
1H NMR (CDCl3): d = 0.85 (t, J = 8 Hz, 3 H), 1.22–1.36 (m, 2 H),
1.57–1.68 (m, 2 H), 2.62 (t, J = 8 Hz, 2 H), 4.79 (q, J = 8 Hz, 2 H),
7.25–7.33 (m, 2 H), 7.51–7.58 (m, 3 H).
In conclusion, we have developed a versatile method for
regioslective synthesis of 1,4,5-trisubstituted 1,2,3-triaz-
oles from 1,4-disubstituted 5-iodo-1,2,3-triazoles 1 by
palladium catalyzed cross-coupling reaction (Suzuki reac- 19F NMR (CDCl3): d = –70.32 (t, J = 8 Hz, 3 F).
MS: m/z (%) = 283 (M+, 3), 264 (1), 212 (57), 103 (100), 91 (7), 77
(16).
tion, Heck reaction and Sonogashira reaction). This meth-
odology provides a general method for the preparation of
various 1,4,5-trisubstituted 1,2,3-triazoles and can be
used for their synthesis via combinational chemistry.
Anal. Calcd for C14H16F3N3: C, 59.36; H, 5.69; N, 14.83. Found: C,
59.26; H, 5.72; N, 14.81.
4-Butyl-5-phenyl-1-(2,2,3,3-tetrafluoropropyl)-1H-1,2,3-tri-
azole (3b)
Yellow liquid.
IR (film): 700, 1109, 1193, 1256, 2959 cm–1.
Melting points and boiling points are uncorrected. IR spectra were
obtained with a Perkin-Elmer 983G spectrometer on KBr disks.
NMR spectra were recorded either on a Varian-360L or Bruker
AM-300 spectrometer with CDCl3 as solvent. Chemical shifts were
Table 4 Results of the Sonogashira Reaction of 1,4-Disubstituted 5-Iodo-1,2,3-triazolesa
N
R1
N
N
N
R1
N
I
N
R5
R2
R2
R5
7
1
6
Entry
1,4-Disubstituted 5-Iodo-1,2,3-triazole 1
Terminal Acetylene 6 Product 7
Yield (%)b
R1
R2
R5
1
2
3
4
5
6
7
8
HCF2CF2CH2
PhCH2
Ph
Ph
Ph
Ph
Ph
Ph
Ph
C4H9
Ph
7a
7b
7c
7d
7e
7f
92
95
73
99
71
63
92
98
Ph
HCF2CF2CH2
PhCH2
C4H9
C4H9
CH2OH
TMS
TMS
Ph
PhCH2
HCF2CF2CH2
PhCH2
7g
7h
HCF2CF2CH2
a Reaction conditions: 1,4-disubstituted 5-iodo-1,2,3-triazole 1 (0.20 mmol), terminal alkyne 6 (0.40 mmol), PdCl2(PPh3)2 (10 mol%), K2CO3
(0.30 mmol), THF (3 mL), reflux.
b Isolated yield based on 1.
Synthesis 2005, No. 16, 2730–2738 © Thieme Stuttgart · New York

2734
J. Deng et al.
PAPER
1H NMR (CDCl3): d = 0.86 (t, J = 7 Hz, 3 H), 1.24–1.37 (m, 2 H),
1.58–1.66 (m, 2 H), 2.67 (t, J = 8 Hz, 2 H), 4.73 (t, J = 13 Hz, 2 H),
6.03 (tt, J = 4, 52 Hz, 1 H), 7.26–7.32 (m, 2 H), 7.50–7.56 (m, 3 H).
19F NMR (CDCl3): d = –138.33 (d, J = 52 Hz, 2 F), –120.58 to
–120.47 (m, 2 F).
1H NMR (CDCl3): d = 5.44 (s, 2 H), 6.99–7.03 (m, 2 H), 7.23–7.30
(m, 8 H), 7.49–7.53 (m, 2 H), 7.64–7.69 (m, 2 H).
19F NMR (CDCl3): d = –63.14 (s, 3 F).
MS: m/z (%) = 379 (M+, 16), 360 (3), 260 (98), 91 (100).
Anal. Calcd for C22H16F3N3: C, 69.65; H, 4.25; N, 11.08. Found: C,
69.54; H, 4.31; N, 11.02.
MS: m/z (%) = 315 (M+, 3), 244 (53), 103 (100), 91 (9), 77 (20).
Anal. Calcd for C15H17F4N3: C, 57.14; H, 5.43; N, 13.33; F, 24.10.
Found: C, 57.03; H, 5.54; N, 13.24; F, 23.97.
4-Butyl-5-(4-methoxyphenyl)-1-(2,2,2-trifluoroethyl)-1H-1,2,3-
triazole (3h)
Colorless liquid.
4,5-Diphenyl-1-(2,2,3,3-tetrafluoropropyl)-1H-1,2,3-triazole
(3c)
IR (film): 847, 1037, 1164, 1252, 1508, 1616, 2862, 2959 cm–1.
Yellow solid; mp 113–114 °C.
IR (KBr): 699, 769, 1110, 1259, 1360, 3029 cm–1.
1H NMR (CDCl3): d = 4.73 (t, J = 13 Hz, 2 H), 6.05 (tt, J = 4, 53
Hz, 1 H), 7.25–7.37 (m, 5 H), 7.50–7.57 (m, 5 H).
19F NMR (CDCl3): d = –138.02 (d, J = 59 Hz, 2 F), –120.09 (t,
J = 14 Hz, 2 F).
1H NMR (CDCl3): d = 0.85 (t, J = 7 Hz, 3 H), 1.23–1.36 (m, 2 H),
1.56–1.67 (m, 2 H), 2.60 (t, J = 8 Hz, 2 H), 3.87 (s, 3 H), 4.77 (q,
J = 8 Hz, 2 H), 7.02–7.06 (m, 2 H), 7.18–7.28 (m, 2 H).
13C NMR (CDCl3): d = 13.69, 22.27, 24.66, 31.55, 48.53, 55.36,
114.74, 118.22, 120.46, 124.17, 127.90, 131.07, 135.48, 146.24,
160.70.
MS: m/z (%) = 335 (M+, 8), 307 (31), 192 (82), 165 (100), 89 (14),
77 (5).
19F NMR (CDCl3): d = –70.32 (t, J = 8 Hz, 3 F).
MS: m/z (%) = 313 (M+, 12), 285 (10), 202 (48), 146 (81), 133
Anal. Calcd for C17H13F4N3: C, 60.90; H, 3.91; N, 12.53. Found: C,
60.98; H, 3.87; N, 12.35.
(100), 77 (18).
HRMS: m/z calcd for C15H18F3N3O: 313.1399; found: 313.1396.
1-Benzyl-4,5-diphenyl-1H-1,2,3-triazole (3d)
Yellow solid; mp 107–108 °C.
IR (KBr): 697, 983, 1354, 1605, 3063 cm–1.
4-Butyl-5-(4-methoxyphenyl)-1-(2,2,3,3-tetrafluoropropyl)-1H-
1,2,3-triazole (3i)
Colorless liquid.
1H NMR (CDCl3): d = 5.43 (s, 2 H), 7.02–7.07 (m, 2 H), 7.14–7.19
(m, 2 H), 7.24–7.30 (m, 6 H), 7.40–7.50 (m, 3 H), 7.56–7.60 (m, 2
H).
IR (film): 846, 1037, 1110, 1178, 1253, 1509, 1616, 2862, 2959
cm–1.
1H NMR (CDCl3): d = 0.87 (t, J = 7 Hz, 3 H), 1.24–1.37 (m, 2 H),
1.57–1.69 (m, 2 H), 2.62 (t, J = 8 Hz, 2 H), 3.90 (s, 3 H), 4.71 (t,
J = 13 Hz, 2 H), 6.05 (tt, J = 4, 53 Hz, 1 H), 7.02–7.07 (m, 2 H),
7.18–7.23 (m, 2 H).
MS: m/z (%) = 311 (M+, 10), 192 (81), 165 (21), 91 (100).
Anal. Calcd for C21H17N3: C, 81.00; H, 5.50; N, 13.49. Found: C,
80.84; H, 5.76; N, 13.37.
13C NMR (CDCl3): d = 13.74, 22.31, 24.70, 31.57, 46.55, 55.39,
109.02, 112.34, 114.72, 118.25, 131.14, 135.98, 146.19, 160.67.
1-Octyl-4,5-diphenyl-1H-1,2,3-triazole (3e)
White solid; mp 55–56 °C.
IR (KBr): 697, 776, 1073, 1355, 1605, 2855, 2926, 3058 cm–1.
19F NMR (CDCl3): d = –138.42 (d, J = 54 Hz, 2 F), –120.74 to
–120.61 (m, 2 F).
1H NMR (CDCl3): d = 0.87 (t, J = 7 Hz, 3 H), 1.18–1.28 (m, 10 H),
1.74–1.82 (m, 2 H), 4.22 (t, J = 7 Hz, 2 H), 7.26–7.31 (m, 3 H),
7.33–7.37 (m, 2 H), 7.52–7.58 (m, 5 H).
MS: m/z (%) = 345 (M+, 8), 317 (9), 202 (38), 146 (63), 133 (100),
77 (7).
HRMS: m/z calcd for C16H19F4N3O: 345.1454; found: 345.1458.
MS: m/z (%) = 333 (M+, 11), 193 (100), 178 (17), 165 (57), 89 (20).
1-Benzyl-5-(4-methoxyphenyl)-4-phenyl-1H-1,2,3-triazole (3j)
Yellow solid; mp 101–102 °C.
IR (KBr): 839, 1177, 1252, 1515, 1614, 2374, 2936, 3032 cm–1.
Anal. Calcd for C22H27N3: C, 79.24; H, 8.16; N, 12.60. Found: C,
78.92; H, 8.15; N, 12.52.
4-Phenyl-1-(2,2,3,3-tetrafluoropropyl)-5-(4-trifluorometh-
ylphenyl)-1H-1,2,3-triazole (3f)
Yellow solid; mp 77–78 °C.
IR (KBr): 697, 854, 1109, 1325, 1406, 1624, 1711 cm–1.
1H NMR (CDCl3): d = 4.75 (t, J = 13 Hz, 2 H), 6.02 (tt, J = 3, 53 Hz,
1 H), 7.26–7.32 (m, 3 H), 7.48–7.52 (m, 4 H), 7.80–7.83 (m, 2 H).
19F NMR (CDCl3): d = –137.54 (d, J = 54 Hz, 2 F), –119.53 (t,
J = 13 Hz, 2 F), –63.22 (s, 3 F).
1H NMR (CDCl3): d = 3.87 (s, 3 H), 5.40 (s, 2 H), 6.91–6.97 (m, 2
H), 7.03–7.09 (m, 4 H), 7.23–7.30 (m, 6 H), 7.55–7.61 (m, 2 H).
MS: m/z (%) = 341 (M+, 6), 235 (19), 222 (44), 206 (66), 116 (94),
91 (100).
Anal. Calcd for C22H19N3O: C, 77.40; H, 5.61; N, 12.31. Found: C,
77.09; H, 5.59; N, 12.21.
1-Benzyl-5-(4-chlorophenyl)-4-phenyl-1H-1,2,3-triazole (3k)
White solid; mp 118–119 °C.
IR (KBr): 695, 731, 838, 1092, 1353, 1505, 2322, 3064 cm–1.
1H NMR (CDCl3): d = 5.41 (s, 2 H), 7.00–7.08 (m, 4 H), 7.25–7.30
(m, 6 H), 7.37–7.42 (m, 2 H), 7.50–7.56 (m, 2 H).
MS: m/z (%) = 403 (M+, 9), 384 (6), 375 (35), 260 (100), 233 (74).
Anal. Calcd for C18H12F7N3: C, 53.61; H, 3.00; N, 10.42. Found: C,
53.47; H, 3.07; N, 10.41.
1-Benzyl-4-phenyl-5-(4-trifluoromethylphenyl)-1H-1,2,3-tri-
azole (3g)
White solid; mp 127–128 °C.
IR (KBr): 699, 851, 1068, 1127, 1169, 1325, 1405, 1622 cm–1.
MS: m/z (%) = 345 (M+, 7), 226 (45), 190 (16), 91 (100).
Anal. Calcd for C21H16ClN3: C, 72.93; H, 4.66; N, 12.15. Found: C,
73.12; H, 4.64; N, 11.93.
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Cross-Coupling Reaction of Iodo-1,2,3-triazoles
2735
5-(Hept-1-enyl)-4-phenyl-1-(2,2,3,3-tetrafluorophenyl)-1H-
1,2,3-triazole (3l)
MS: m/z (%) = 343 (M+, 27), 324 (7), 314 (27), 214 (100), 140 (74),
115 (72), 111 (40), 77 (35).
Yellow liquid.
IR (film): 695, 838, 1092, 1505, 1603, 3064 cm–1.
Anal. Calcd for C15H13F4N3O2: C, 52.48; H, 3.82; N, 12.24; F,
22.14. Found: C, 52.32; H, 3.87; N, 12.15; F, 22.14.
1H NMR (CDCl3): d = 0.91 (t, J = 7 Hz, 3 H), 1.28–1.38 (m, 4 H),
1.41–1.52 (m, 2 H), 2.26 (q, J = 7 Hz, 2 H), 4.87 (t, J = 13 Hz, 2 H),
6.03 (tt, J = 3, 53 Hz, 1 H), 6.08–6.23 (m, 1 H), 6.28 (d, J = 16 Hz,
1 H), 7.32–7.45 (m, 3 H), 7.76–7.79 (m, 2 H).
13C NMR (CDCl3): d = 13.85, 22.38, 28.18, 31.24, 33.37, 46.63,
109.21, 112.53, 113.88, 127.56, 128.10, 128.56, 131.03, 132.97,
142.99, 144.32.
(E)-3-(1-Benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)acrylic Acid
Methyl Ester [(E)-5b]
White solid; mp 85–86 °C.
IR (KBr): 697, 1175, 1271, 1646, 1719, 2950, 3032 cm–1.
1H NMR (CDCl3): d = 3.75 (s, 3 H), 5.70 (s, 2 H), 6.23 (d, J = 16
Hz, 1 H), 7.21–7.27 (m, 2 H), 7.33–7.51 (m, 6 H), 7.60 (d, J = 16
Hz, 1 H), 7.63–7.69 (m, 2 H).
19F NMR (CDCl3): d = –137.63 (d, J = 53 Hz, 2 F), –119.88 (t,
J = 12 Hz, 2 F).
MS: m/z (%) = 319 (M+, 14), 288 (2), 200 (85), 140 (24), 91 (100),
69 (37), 43 (34).
MS: m/z (%) = 385 (M+, 3), 355 (16), 336 (2), 270 (100), 212 (45),
142 (68), 128 (84), 115 (46).
Anal. Calcd for C19H17N3O2: C, 71.46; H, 5.37; N, 13.16. Found: C,
71.27; H, 5.44; N, 12.94.
HRMS: m/z calcd for C18H21F4N3: 355.1651; found: 355.1662.
(E)-4-[4-Phenyl-1-(2,2,3,3-tetrafluoropropyl)-1H-1,2,3-triazol-
5-yl]but-3-en-2-one [(E)-5c]
Yellow liquid.
IR (film): 699, 1108, 1255, 1361, 1620, 1675, 1698, 3011 cm–1.
1H NMR (CDCl3): d = 2.31 (s, 3 H), 5.03 (t, J = 14 Hz, 2 H), 6.02
(tt, J = 3, 53 Hz, 1 H), 6.66 (d, J = 17 Hz, 1 H), 7.42–7.53 (m, 4 H),
7.64–7.69 (m, 2 H).
19F NMR (CDCl3): d = –136.55 (d, J = 53 Hz, 2 F), –118.73 (t,
J = 14 Hz, 2 F).
1-Benzyl-5-(hept-1-enyl)-4-phenyl-1H-1,2,3-triazole (3m)
Colorless liquid.
IR (film): 697, 729, 1456, 1496, 1606, 2928, 3032 cm–1.
1H NMR (CDCl3): d = 0.88 (t, J = 7 Hz, 3 H), 1.28–1.40 (m, 6 H),
2.15 (q, J = 7 Hz, 2 H), 5.57 (s, 2 H), 5.92–6.03 (m, 1 H), 6.19 (d,
J = 16 Hz, 1 H), 7.17–7.23 (m, 2 H), 7.32–7.46 (m, 6 H), 7.76–7.80
(m, 2 H).
13C NMR (CDCl3): d = 13.95, 22.42, 28.26, 31.21, 33.33, 52.11,
114.61, 127.07, 127.56, 127.78, 128.11, 128.51, 128.89, 131.32,
131.72, 135.52, 140.98.
MS: m/z (%) = 327 (M+, 23), 308 (3), 298 (28), 284 (35), 198 (100),
115 (85), 91 (77), 43 (59).
MS: m/z (%) = 331 (M+, 19), 212 (78), 142 (39), 91 (100).
Anal. Calcd for C15H13F4N3O: C, 55.05; H, 4.00; N, 12.84. Found:
C, 54.71; H, 4.23; N, 12.43.
HRMS: m/z calcd for C22H25N3 331.2047; found: 331.2042.
1-Benzyl-5-(3-benzyloxypropenyl)-4-phenyl-1H-1,2,3-triazole
(3n)
Colorless liquid.
IR (film): 698, 732, 1115, 1361, 1455, 1496, 1606, 2853, 3031 cm–1.
1H NMR (CDCl3): d = 4.07–4.14 (m, 2 H), 4.48 (s, 2 H), 5.59 (s, 2
H), 7.60–7.14 (m, 1 H), 6.54 (d, J = 16 Hz, 1 H), 7.18–7.23 (m, 2
H), 7.26–7.47 (m, 11 H), 7.71–7.77 (m, 2 H).
(E)-4-(1-Benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)but-3-en-2-one
[(E)-5d]
White solid; mp 123–124 °C.
IR (KBr): 699, 1178, 1252, 1360, 1619, 1671, 1679, 3032 cm–1.
1H NMR (CDCl3): d = 2.20 (s, 3 H), 5.70 (s, 2 H), 6.49 (d, J = 17
Hz, 1 H), 7.21–7.69 (m, 11 H).
MS: m/z (%) = 303 (M+, 26), 274 (12), 184 (86), 91 (100), 53 (48).
MS: m/z (%) = 381 (M+, 3), 352 (3), 91 (100), 77 (6).
Anal. Calcd for C19H17N3O: C, 75.23; H, 5.65; N, 13.85. Found: C,
55.28; H, 5.69; N, 13.88.
Anal. Calcd for C25H23N3O: C, 78.71; H, 6.08; N, 11.02. Found: C,
78.25; H, 6.06; N, 10.90.
(E)-4-[4-Butyl-1-(2,2,3,3-tetrafluoropropyl)-1H-1,2,3-triazol-5-
yl]but-3-en-2-one [(E)-5e]
Yellow liquid.
IR (film): 1108, 1254, 1617, 1674, 2961 cm–1.
1H NMR (CDCl3): d = 0.97 (t, J = 7 Hz, 3 H), 1.37–1.51 (m, 2 H),
1.66–1.83 (m, 2 H), 2.40 (s, 3 H), 2.84 (t, J = 8 Hz, 2 H), 4.97 (t,
J = 14 Hz, 2 H), 5.95 (tt, J = 3, 53 Hz, 1 H), 6.64 (d, J = 16 Hz, 1
H), 7.39 (d, J = 16 Hz, 1 H).
Heck Reaction of 1,4-Disubstituted 5-Iodo-1,2,3-triazoles 1;
General Procedure
Under N2, to a Schlenk tube, triazole 1 (0.20 mmol), terminal alkene
4 (0.50 mmol), Pd(OAc)2 (0.020 mmol, 10%), TBAB (0.08 mmol),
NaHCO3 (0.50 mmol), DMF (3 mL) were added successively. The
mixture was stirred at 80 °C for 4 or 24 h. After removal of solvent,
the crude product was purified by flash chromatography on a silicon
gel column with hexane–EtOAc (5:1) as eluent.
13C NMR (CDCl3): d = 13.81, 22.48, 26.16, 28.57, 29.70, 30.33,
(E)-3-[4-Phenyl-1-(2,2,3,3-tetrafluoropropyl)-1H-1,2,3-triazol-
5-yl]acrylic Acid Methyl Ester [(E)-5a]
White solid; mp 80–81 °C.
IR (KBr): 699, 1107, 1201, 1650, 1720, 2957, 3011 cm–1.
1H NMR (CDCl3): d = 3.82 (s, 3 H), 5.03 (t, J = 13 Hz, 2 H), 6.04
(tt, J = 3, 53 Hz, 1 H), 6.40 (d, J = 16 Hz, 1 H), 7.42–7.73 (m, 3 H),
7.57–7.70 (m, 3 H).
47.04, 105.85, 109.17, 124.86, 130.48, 134.41, 148.65, 196.63.
19F NMR (CDCl3): d = –136.65 (d, J = 53 Hz, 2 F), –118.99 (t,
J = 14 Hz, 2 F).
MS: m/z (%) = 307 (M+, 15), 288 (5), 264 (100), 250 (95), 186 (76),
95 (98), 43 (62).
HRMS: m/z calcd for C13H17F4N3O: 307.1304; found: 307.1302.
19F NMR (CDCl3): d = –136.64 (d, J = 53 Hz, 2 F), –119.02 (t,
J = 14 Hz, 2 F).
(E)-4-(1-Benzyl-4-butyl-1H-1,2,3-triazol-5-yl)but-3-en-2-one
[(E)-5f]
Yellow liquid.
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2736
J. Deng et al.
PAPER
IR (film): 731, 970, 1252, 1359, 1456, 1615, 1671, 2957 cm–1.
(E)-3-(1-Benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)propenal [(E)-
5i]
1H NMR (CDCl3): d = 0.96 (t, J = 7 Hz, 3 H), 1.35–1.50 (m, 2 H),
1.67–1.81 (m, 2 H), 2.26 (s, 3 H), 2.80 (t, J = 8 Hz, 2 H), 5.63 (s, 2
H), 6.47 (d, J = 17 Hz, 1 H), 7.15–7.20 (m, 2 H), 7.27–7.40 (m, 4
H).
MS: m/z = 283 (M+, 5), 255 (1), 240 (20), 164 (11), 91 (100), 65 (9),
43 (6).
Colorless liquid.
1H NMR (CDCl3): d = 5.75 (s, 2 H), 6.48 (dd, J = 8, 16 Hz, 1 H),
7.17–7.22 (m, 2 H), 7.30–7.44 (m, 4 H), 7.44–7.52 (m, 3 H), 7.62–
7.68 (m, 2 H), 9.54 (d, J = 8 Hz, 1 H).
13C NMR (CDCl3): d = 53.21, 126.80, 127.27, 127.52, 128.515,
128.79, 128.96, 129.08, 129.15, 129.24, 129.30, 129.37, 130.11,
131.46, 132.02, 134.16, 134.32, 192.35.
Anal. Calcd for C17H21N3O: C, 72.06; H, 7.47; N, 14.83. Found: C,
72.09; H, 7.43; N, 14.46.
MS: m/z (%) = 289 (M+, 25), 260 (22), 170 (100), 142 (25), 91 (93),
(Z/E)-3-[4-Phenyl-1-(2,2,3,3-tetrafluoropropyl)-1H-1,2,3-tri-
azol-5-yl]acrylonitriles [(Z)-5g and (E)-5g¢]
(Z)-5g
39 (41).
HRMS: m/z calcd for C18H15N3O: 289.1209; found: 289.1210.
White solid; mp 85–86 °C.
IR (KBr): 1110, 1212, 1492, 1519, 1629, 1697, 2225, 3012 cm–1.
(E)-1-Benzyl-4-phenyl-5-styryl-1H-1,2,3-triazole [(E)-5j]
White solid; mp 85–86 °C.
1H NMR (CDCl3): d = 5.03 (t, J = 14 Hz, 2 H), 5.95 (d, J = 11 Hz,
1 H), 5.97 (tt, J = 3, 53 Hz, 1 H), 7.29 (d, J = 11 Hz, 1 H), 7.42–7.54
(m, 3 H), 7.68–7.72 (m, 2 H).
19F NMR (CDCl3): d = –136.38 (d, J = 53 Hz, 2 F), –118.78 (t,
J = 14 Hz, 2 F).
IR (KBr): 695, 730, 1496, 1606, 3031 cm–1.
1H NMR (CDCl3): d = 5.66 (s, 2 H), 6.76–6.91 (m, 2 H), 7.22–7.46
(m, 13 H), 7.75–7.82 (m, 2 H).
13C NMR (CDCl3): d = 52.51, 112.60, 126.75, 127.16, 127.81,
128.06, 128.15, 128.40, 128.77, 128.93, 129.00, 129.10, 131.07,
131.50, 135.46, 135.81, 136.63.
MS: m/z (%) = 310 (M+, 3), 291 (3), 282 (12), 181 (100), 167 (83),
140 (59), 51 (16).
MS: m/z (%) = 337 (M+, 32), 218 (53), 140 (64), 115 (100), 91
Anal. Calcd for C14H10F4N4: C, 54.20; H, 3.25; N, 18.06. Found: C,
54.01; H, 3.12; N, 18.49.
(100), 65 (23).
HRMS: m/z calcd for C23H19N3: 337.1556; found: 337.1573.
(E)-5g¢
Sonogashira Reaction of 1,4-Disubstituted 5-Iodo-1,2,3-tri-
azoles 1; General Procedure
White solid; mp 111–112 °C.
IR (KBr): 700, 1108, 1360, 1628, 2224, 3013 cm–1.
Under N2, to a Schlenk tube, triazole 1 (0.20 mmol), terminal alkyne
6 (0.40 mmol), PdCl2(PPh3)2 (0.020 mmol, 10%), K2CO3 (0.30
mmol), THF (3 mL) were added successively. The mixture was
stirred at 70 °C for 4–5 h. After removal of solvent, the crude prod-
uct was purified by flash chromatography on a silicon gel column
with hexane–EtOAc (5:1) as eluent.
1H NMR (CDCl3): d = 5.00 (t, J = 14 Hz, 2 H), 5.87 (d, J = 17 Hz,
1 H), 6.02 (tt, J = 3, 53 Hz, 1 H), 7.30 (d, J = 17 Hz, 1 H), 7.48–7.56
(m, 3 H), 7.58–7.65 (m, 2 H).
19F NMR (CDCl3): d = –136.00 (d, J = 54 Hz, 2 F), –118.30 (t,
J = 14 Hz, 2 F).
MS: m/z (%) = 310 (M+, 14), 181 (80), 167 (100), 140 (78), 51 (45).
4-Phenyl-5-phenylethynyl-1-(2,2,3,3-tetrafluoropropyl)-1H-
1,2,3-triazole (7a)
Yellow solid; mp 92–93 °C.
IR (KBr): 690, 1109, 1362, 2222, 3066 cm–1.
Anal. Calcd for C14H10F4N4: C, 54.20; H, 3.25; N, 18.06. Found: C,
54.08; H, 3.21; N, 17.89.
1H NMR (CDCl3): d = 5.07 (t, J = 13 Hz, 2 H), 6.02 (tt, J = 3, 53
Hz, 1 H), 7.37–7.53 (m, 6 H), 7.56–7.62 (m, 2 H), 8.19–8.24 (m, 2
H).
19F NMR (CDCl3): d = –136.75 (d, J = 53 Hz, 2 F), –119.15 (t,
J = 13 Hz, 2 F).
(Z/E)-3-(1-Benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)acrylonitriles
[(Z)-5h and (E)-5h¢]
(Z)-5h
White solid; mp 84–85 °C.
IR (KBr): 696, 724, 1010, 1349, 2223, 3035 cm–1.
1H NMR (CDCl3): d = 5.69 (d, J = 11 Hz, 1 H), 5.70 (s, 2 H), 6.98
(d, J = 11 Hz, 1 H), 7.14–7.22 (m, 2 H), 7.30–7.48 (m, 6 H), 7.62–
7.70 (m, 2 H).
MS: m/z (%) = 359 (M+, 24), 331 (25), 216 (100), 189 (47), 101 (5),
51 (10).
Anal. Calcd for C19H13F4N3: C, 63.51; H, 3.65; N, 11.69. Found: C,
63.45; H, 3.73; N, 11.68.
MS: m/z (%) = 286 (M+, 13), 257 (17), 167 (100), 91 (26), 65 (10).
Anal. Calcd for C18H14N4: C, 75.50; H, 4.93; N, 19.57. Found: C,
75.58; H, 4.92; N, 19.78.
1-Benzyl-4-phenyl-5-phenylethynyl-1H-1,2,3-triazole (7b)
Yellow solid; mp 91–92 °C.
IR (KBr): 691, 1357, 2220, 3064 cm–1.
1H NMR (CDCl3): d = 5.68 (s, 2 H), 7.33–7.54 (m, 13 H), 8.16–8.21
(m, 2 H).
(E)-5h¢
White solid; mp 103–104 °C.
IR (KBr): 699, 730, 1009, 1354, 2220, 3064 cm–1.
1H NMR (CDCl3): d = 5.67 (d, J = 15 Hz, 1 H), 5.69 (s, 2 H), 7.18–
7.28 (m, 3 H), 7.38–7.54 (m, 6 H), 7.58–7.64 (m, 2 H).
MS: m/z (%) = 335 (M+, 21), 216 (100), 189 (34), 91 (41).
Anal. Calcd for C23H17N3: C, 82.36; H, 5.11; N, 12.53. Found: C,
81.83; H, 5.15; N, 12.51.
MS: m/z (%) = 286 (M+, 10), 257 (8), 167 (100), 91 (57), 65 (25).
Anal. Calcd for C18H14N4: C, 75.50; H, 4.93; N, 19.57. Found: C,
75.41; H, 4.74; N, 19.46.
5-(Hex-1-ynyl)-4-phenyl-1-(2,2,3,3-tetrafluoropropyl)-1H-
1,2,3-triazole (7c)
Colorless liquid.
Synthesis 2005, No. 16, 2730–2738 © Thieme Stuttgart · New York

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Cross-Coupling Reaction of Iodo-1,2,3-triazoles
2737
IR (film): 694, 1111, 1362, 2237, 2961 cm–1.
4-Butyl-5-phenylethynyl-1-(2,2,3,3-tetrafluoropropyl)-1H-
1,2,3-triazole (7h)
Yellow liquid.
IR (film): 689, 757, 1111, 2226, 2959 cm–1.
1H NMR (CDCl3): d = 0.98 (t, J = 7 Hz, 3 H), 1.49–1.59 (m, 2 H),
1.61–1.73 (m, 2 H), 2.60 (t, J = 7 Hz, 2 H), 4.97 (t, J = 13 Hz, 2 H),
5.98 (tt, J = 3, 53 Hz, 1 H), 7.35–7.50 (m, 3 H), 8.14–8.17 (m, 2 H).
13C NMR (CDCl3): d = 13.38, 19.43, 21.92, 30.03, 30.78, 46.88,
66.30, 105.86, 109.23, 113.67, 119.67, 126.05, 128.65, 129.87,
147.09.
1H NMR (CDCl3): d = 0.96 (t, J = 7 Hz, 3 H), 1.34–1.48 (m, 2 H),
1.72–1.84 (m, 2 H), 2.83 (t, J = 8 Hz, 2 H), 4.97 (t, J = 13 Hz, 2 H),
5.97 (tt, J = 3, 53 Hz, 1 H), 7.36–7.46 (m, 3 H), 7.51–7.56 (m, 2 H).
19F NMR (CDCl3): d = –137.16 (d, J = 52 Hz, 2 F), –119.69 (t,
J = 12 Hz, 2 F).
MS: m/z (%) = 339 (M+, 39), 311 (34), 268 (8), 127 (100), 115 (27),
13C NMR (CDCl3): d = 13.79, 22.24, 25.29, 30.84, 47.17, 102.09,
105.93, 109.26, 112.57, 113.67, 114.06, 121.19, 128.68, 129.79,
131.59.
19F NMR (CDCl3): d = –137.13 (d, J = 54 Hz, 2 F), –119.53 (t,
J = 14 Hz, 2 F).
91 (34), 77 (28).
HRMS: m/z calcd for C17H17FN3: 339.1352; found: 339.1353.
MS: m/z (%) = 339 (M+, 23), 310 (9), 268 (29), 127 (100), 115 (15),
1-Benzyl-5-(hex-1-ynyl)-4-phenyl-1H-1,2,3-triazole (7d)
91 (6), 77 (10).
Colorless liquid.
IR (film): 695, 1357, 2235, 2957 cm–1.
HRMS: m/z calcd for C17H17FN3: 339.1349; found: 339.1353.
1H NMR (CDCl3): d = 0.94 (t, J = 7 Hz, 3 H), 1.39–1.49 (m, 2 H),
1.54–1.64 (m, 2 H), 2.53 (t, J = 7 Hz, 2 H), 5.59 (s, 2 H), 7.30–7.46
(m, 8 H), 8.11–8.16 (m, 2 H).
Acknowledgment
The authors thank the National Natural Science Foundation of Chi-
na (NNSFC) (No. 20472104) and Shanghai Science and Technolo-
gy Committee (Project No.: 035211018) for partial financial
support.
MS: m/z (%) = 315 (M+, 38), 196 (100), 91 (41), 77 (8).
Anal. Calcd for C21H21N3: C, 79.97; H, 6.71; N, 13.32. Found: C,
80.05; H, 6.76; N, 12.84.
3-(3-Benzyl-5-phenyl-3H-1,2,3-triazol-4-yl)prop-2-yn-1-ol (7e)
White solid; mp 100–101 °C.
References
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F.; Stang, P. J., Eds.; Wiley-VCH: Weinheim, 1998.
(b) Tsuji, J. Transition Metal Reagents and Catalysts:
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(c) Miyaura, N. Top. Curr. Chem. 2002, 219, 1.
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Perspectives for the 21st Century; Wiley: Chichester, 2004.
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A. J. Org. Chem. 2003, 68, 3327.
IR (KBr): 695, 1039, 1355, 1497, 1702, 3345 cm–1.
1H NMR (CDCl3): d = 1.91 (t, J = 6 Hz, 1 H), 4.57 (d, J = 6 Hz, 2
H), 5.59 (s, 2 H), 7.30–7.47 (m, 8 H), 8.05–8.11 (m, 2 H).
MS: m/z (%) = 289 (M+, 44), 170 (100), 115 (26), 91 (81), 77 (16),
65 (20), 39 (57).
Anal. Calcd for C18H15N3O: C, 74.72; H, 5.23; N, 14.52. Found: C,
74.68; H, 5.28; N, 14.54.
4-Phenyl-1-(2,2,3,3-tetrafluoropropyl)-5-trimethylsilylethynyl-
1H-1,2,3-triazole (7f)
White solid; mp 61–62 °C.
IR (KBr): 693, 845, 1110, 1253, 2166, 2963 cm–1.
1H NMR (CDCl3): d = 0.32 (s, 9 H), 5.00 (t, J = 14 Hz, 2 H), 5.98
(tt, J = 3, 53 Hz, 1 H), 7.36–7.51 (m, 3 H), 8.15–8.20 (m, 2 H).
13C NMR (CDCl3): d = –0.67, 46.99, 89.40, 105.98, 109.28, 111.66,
119.01, 126.26, 128.68, 128.98, 129.61, 148.04.
19F NMR (CDCl3): d = –136.80 (d, J = 53 Hz, 2 F), –119.21 (t,
J = 14 Hz, 2 F).
MS: m/z (%) = 355 (M+, 43), 336 (3), 327 (100), 108 (38), 212 (18),
(6) Dakin, L. A.; Langille, N. F.; Panek, J. S. J. Org. Chem.
2002, 67, 6812.
77 (17).
(7) Branu, R. U.; Zeilter, K.; Muller, T. J. J. Org. Lett. 2001, 3,
3297.
HRMS: m/z calcd for C16H17F4N3Si: 355.1115; found: 355.1122.
(8) Sarkar, A.; Okada, S.; Nakanishi, H.; Matsuda, H. Helv.
1-Benzyl-4-phenyl-5-trimethylsilylethynyl-1H-1,2,3-triazole
(7g)
Chim. Acta 1999, 82, 138.
(9) Yue, D.; Larock, R. C. J. Org. Chem. 2002, 67, 1905.
(10) (a) Ohta, A.; Akita, Y.; Ohkuwa, T.; Chiba, M.; Fukunaga,
R.; Miyafuji, A.; Nakata, T.; Tani, N.; Aoyagi, Y.
Heterocycles 1990, 31, 1951. (b) Aoyagi, Y.; Inoue, A.;
Koizumi, I.; Hashimoto, R.; Tokunaga, K.; Gohma, K.;
Komatsu, J.; Sekine, K.; Miyafuji, A.; Kunoh, J.; Honma, R.;
Akita, Y.; Ohta, A. Heterocycles 1992, 33, 257.
(11) Gelman, D.; Tsvelikhovsky, D.; Molander, G. A.; Blum, J.
J. Org. Chem. 2002, 67, 6287.
White solid; mp 65–66 °C.
IR (KBr): 695, 846, 1251, 2163, 2959 cm–1.
1H NMR (CDCl3): d = 0.28 (s, 9 H), 5.60 (s, 2 H), 7.30–7.44 (m, 8
H), 8.11–8.16 (m, 2 H).
13C NMR (CDCl3) d = –0.54, 52.91, 90.82, 110.31, 117.14, 126.15,
128.24, 128.46, 128.54, 128.59, 128.78, 128.93, 130.23, 134.71,
148.41.
MS: m/z (%) = 331 (M+, 45), 212 (100), 109 (22), 91 (85).
(12) Tan, J. Q.; Chang, J. H.; Demg, M. Z. Chinese J. Chem.
2004, 22, 941; Chem. Abstr. 2004, 140, 145997.
HRMS: m/z calcd for C20H21N3Si: 331.1499; found: 331.1499.
Synthesis 2005, No. 16, 2730–2738 © Thieme Stuttgart · New York

2738
J. Deng et al.
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