Copper-catalyzed decarboxylation/cycloaddition cascade of alkynyl carboxylic acids with azide

Article abstract of DOI:10.1016/j.tet.2018.11.054

A copper-catalyzed decarboxylation/cycloaddition cascade of alkynyl carboxylic acids with azide has been developed. This reaction exhibits good functional group tolerance and wide substrate scope, provides an efficient way to construct 1,4-disubstituted 1

Full text of DOI:10.1016/j.tet.2018.11.054

Accepted Manuscript
Copper-catalyzed decarboxylation/cycloaddition cascade of alkynyl carboxylic acids
with azide
Jia-Qi Shang, Hong Fu, Yi Li, Tao Yang, Chuanzhu Gao, Ya-Min Li
PII:
S0040-4020(18)31423-6
https://doi.org/10.1016/j.tet.2018.11.054
TET 29965
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 16 October 2018
Revised Date: 21 November 2018
Accepted Date: 24 November 2018
Please cite this article as: Shang J-Q, Fu H, Li Y, Yang T, Gao C, Li Y-M, Copper-catalyzed
decarboxylation/cycloaddition cascade of alkynyl carboxylic acids with azide, Tetrahedron (2018), doi:
https://doi.org/10.1016/j.tet.2018.11.054.
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Copper-catalyzed
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decarboxylation/cycloaddition cascade of
alkynyl carboxylic acids with azide
Jia-Qi Shang, Hong Fu, Yi Li, Tao Yang, Chuanzhu Gao, Ya-Min Li*
a Faculty of Life Science and Technology, Kunming University of Science and Technology, Kunming 650500, P.
R. China

ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Copper-catalyzed decarboxylation/cycloaddition cascade of alkynyl carboxylic acids
with azide
Jia-Qi Shang†, Hong Fu†, Yi Li, Tao Yang, Chuanzhu Gao, Ya-Min Li
Faculty of Life Science and Technology, Kunming University of Science and Technology, Kunming 650500, P. R. China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A copper-catalyzed decarboxylation/cycloaddition cascade of alkynyl carboxylic acids with
azide has been developed. This reaction exhibits good functional group tolerance and wide
substrate scope, provides an efficient way to construct 1,4-disubstituted 1,2,3-triazoles.
2009 Elsevier Ltd. All rights reserved.
Available online
Keywords:
Decarboxylation
Cycloaddition
1,2,3-Triazole
Alkynyl carboxylic acid
Azide
propiolic acids, diselenides and azides.9 On the basis of our
continuing interest in decarboxylative coupling,10 herein we
1. Introduction
1,2,3-Triazoles are well-known highly valuable N-
heterocyclic compounds that are ubiquitous in many
pharmaceuticals and bioactive molecules.1 In light of their
importance, a number of methods have been developed for the
synthesis of 1,2,3-triazoles,2,3 and among them, the copper(I)-
catalyzed 1,3-dipolar cycloaddition of azide and terminal alkyne
(CuAAC) is the most prevailing one due to the wide substrate
scope, exclusive regioselectivity, very high yields, and mild
reaction conditions.3 Decarboxylative coupling reactions is one
of the most powerful methods for the formation of C−C and
C−heteroatom bonds.4,5 Recently, the use of alkynyl carboxylic
acids as terminal alkyne surrogates has attracted significant
attention because alkynyl carboxylic acids are convenient to
synthesize, store, and transport.6,7 For example, alkynes of low
molecular weight are difficult to handle due to their low boiling
points. However, the corresponding alkynoic acids, even the
most simple propiolic acid, has a very high boiling point and can
be easily handled. In this context, copper-catalyzed AAC
reactions involving decarboxylation of alkynyl carboxylic acids
have been developed. Kolarovič et al. reported an efficient Cu-
catalyzed three-component reaction of alkynyl carboxylic acids,
aryl iodides, and sodium azide for the formation of 1,2,3-
triazoles.8 Pan, Xu and co-workers developed a novel Cu-
catalyzed decarboxylative/cycloaddition reaction for the
report a Cu-catalyzed decarboxylation/cycloaddition cascade of
alkynyl carboxylic acids with organic azides.
2. Results and discussions
Initially,
phenylpropiolic
acid
(1a)
and
(azidomethyl)trimethylsilane (2a) were chosen as the model
substrates to optimize reaction conditions for the
decarboxylation/cycloaddition cascade. When phenylpropiolic
acid was treated with 3.0 equiv of (azidomethyl)trimethylsilane
in the presence of 10 mol% of CuBr2 in DMF at 80 °C for 12 h,
the reaction proceeded smoothly and afforded the desired 1,4-
disubstituted 1,2,3-triazole 3aa in 10% yield (Table 1, entry 1).
Subsequently, various copper catalysts such as CuO, Cu(OAc)2,
CuSO4·5H2O, CuBr, CuCl, Cu2O and CuNO3(PPh3)2 were
investigated, and Cu2O gave the best yield (94%) of 3aa (Table
1, entries 2–8). Different solvents were investigated, and CH3CN
was proved to be better than the other solvents (Table 1, entries
9–16). Notably, this transformation could occur in H2O or under
solvent free conditions, leading to product in 90% or 91% yield,
respectively. The effect of azide stoichiometry and the catalyst
loading were also examined, and the results indicate that 5 mol%
of catalyst with 1.0 equiv of azide was the best choice (Table 1,
entries 17–18). Decreasing the temperature negatively affected
the reaction (Table 1, entry 19).
preparation of 1,4-disubstituted 5-arylselanyl-1,2,3-triazoles from
———
 Corresponding author. Tel.: +86 871 65920747; Fax: +86-871-65920570; E-mail address: liym@kmust.edu.cn (Y.-M. Li).
† These authors contributed equally.

2
Tetrahedron
ACCEPTED MANUSCRIPT
Table 1. Optimization of reaction conditions. a
c The reaction was carried out in the presence of 7.0 mmol of 1a.
With the optimized reaction conditions, a variety of organic
azides were subjected to the optimized conditions to evaluate the
scope of the decarboxylation/cycloaddition cascade, and the
results are summarized in Table 2. Alkyl azides, such as
(azidomethyl)trimethylsilane, benzyl azide, ethyl 2-azidoacetate
and 2-azidoethanol, were suitable substrates, affording the
desired products 3aa−3ad in satisfactory yields. In addition, this
transformation could be readily scaled up with similar efficiency.
The reaction of 7.0 mmol of phenylpropiolic acid with ethyl 2-
azidoacetate under the standard reaction conditions gave 1.42 g
of the desired product 3ac in 88% yield. Both electron-rich and -
poor azidobenzenes could be transferred to the 1,4-disubstituted
1,2,3-triazole 3ae−3ao in moderate to excellent yields, and a
series of functional groups, such as methyl, methoxyl, halides,
hydroxyl, and nitrile, were compatible with the reaction
conditions. Moreover, 2-azidonaphthalene was also compatible
with this transformation, albeit in a moderate yield (3ap). It was
pleasant to find that heterocyclesubstituted azide, methyl 2-
azidothiophene-3-carboxylate, provided the corresponding 1,2,3-
Entry 2a (equiv)
Catalyst (equiv)
CuBr2 (10)
CuO (10)
Cu(OAc)2 (10)
CuSO4·5H2O (10)
CuBr (10)
CuCl (10)
Cu2O (10)
CuNO3(PPh3)2 (10)
Cu2O (10)
Solvent
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
Yield (%)b
1
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1
1
1
10
15
89
85
84
80
94
92
92
96
91
49
97
92
91
90
97
2
3
4
5
6
7
8
9
THF
10
11
12
13
14
15
16
17
18
19c
Cu2O (10)
Cu2O (10)
Cu2O (10)
Cu2O (10)
Cu2O (10)
Cu2O (10)
Cu2O (10)
Cu2O (10)
Acetone
DMSO
DCE
CH3CN
Toluene
H2O
-
CH3CN
CH3CN
CH3CN
Cu2O (5)
Cu2O (5)
97
94 (93)d
triazole
3aq
in
good
yield.
However,
4-
acetamidobenzenesulfonyl azide, diphenyl phosphorazidate,
azidotrimethylsilane, benzoyl azide and sodium azide were not
suitable substrates (3ar−3au).
a Reaction conditions: 1a (0.30 mmol), 2a and catalyst in solvent (3 mL) at
80 °C for 12 h under an air atmosphere.
b Isolated yield.
c 70 °C.
d 70 °C, 24 h.
The scope of alkynyl carboxylic acids was also examined. As
shown in Table 3, phenylglyoxylic acids bearing an electron-
donating group (MeO, Me, OH) or an electron-withdrawing
group (CN, F, NO2) at the aryl ring were consistent with the
optimized conditions, and the corresponding products 3ba−3ja
were obtained in moderate to good yields. However, ortho-Cl
substituted phenylpropiolic acid, 3-(naphthalen-2-yl)propiolic
acid, and thienylpropiolic acid were not suitable substrates (3ka-
3ma). In addition, this transformation is not limited to
arylpropiolic acids, alkylpropiolic acids such as propiolic acid,
hex-2-ynoic acid, oct-2-ynoic acid, and 3-cyclopropylpropiolic
acid also reacted well with azidobenzene, giving the
correspondin products 3ne-3qe in moderate to excellent yields.
Table 2. Scope of azides.a,b
Table 3. Scope of alkynyl carboxylic acids.a,b
a All the reactions were carried out in the presence of 0.30 mmol of 1a, 1.0
equiv of 2 and 5 mol% Cu2O in 3.0 mL of CH3CN at 80 °C under an air
atmosphere.
b Isolated yield.

a All the reactions were carried out in the presence of 0.30 mmol of 1, 1.0
3. Conclusion
ACCEPTED MANUSCRIPT
equiv of azide and 5 mol% Cu2O in 3.0 mL of CH3CN at 80 °C under an air
In summary, we have developed
a copper-catalyzed
atmosphere.
b Isolated yield.
decarboxylation/cycloaddition cascade of alkynyl carboxylic
acids with azide. It shows a wide substrate scope and good
functional group compatibility, thus providing a convenient
approach to prepare a variety of 1,4-disubstituted 1,2,3-triazoles.
This transformation could also occur in H2O or under solvent free
conditions. Further investigations toward the reaction scope, and
applications in organic synthesis are currently ongoing in our
laboratory.
When the solvent, CH3CN, were replaced by H2O, the reaction
could be achieved. As shown in Table 4, a variety of alkynyl
carboxylic acids reacted well with azides, provided the
corresponding 1,2,3-triazoles in moderate to excellent yields
(3aa, 3ad, 3an, 3ea, 3fa, 3ja, and 3oe). This transformation
could also occur under solvent free conditions, albeit in moderate
yields (3aa, 3ja, 3da, 3ia, 3ag, and 3pe). However, when
phenylpropiolic acid was treated with ethyl 2-azidoacetate under
solvent free conditions, only trace amounts of product 3ac were
detected.
4. Experimental Section
4.1. General
1H NMR, 13C NMR and spectra were recorded on Bruker
Table 4. Synthesis of 1,2,3-triazoles in H2O or under solvent free conditions.a
AVANCE III HD 600 (600 MHz for H; 151 MHz for 13C)
1
instruments internally referenced to tetramethylsilane (TMS)
signal. Chemical shifts (δ) and coupling constants (J) were
expressed in ppm and Hz, respectively. CDCl3, DMSO-d6, or
CD3OD was used as the NMR solvent in all cases. Mass spectra
were mearsured using Thermo LTQ Orbitrap XL spectrometer.
Unless otherwise noted, materials were obtained from
commercial suppliers and used without further purification.
Alkynyl carboxylic acids11 and organic azides12 were all prepared
following literature procedures. Column chromatography was
carried out on silica gel (particle size 200-300 mesh ASTM).
4.2. General procedures for copper-catalyzed
decarboxylation/cycloaddition cascade of alkynyl carboxylic
acids with azide
In a Schlenk tube, alkynyl carboxylic acid 1 (0.3 mmol), azide
2 (0.3 mmol), Cu2O (0.015 mmol), and CH3CN (3 mL) were
added. The mixture was allowed to stir at 80 °C for 12 hours.
After substrate was consumed, the reaction mixture was cooled to
room temperature and concentrated in vacuum, then purified by
flash chromatography on silica gel with petroleum ether/ethyl
acetate as the eluent to afford the corresponding product 3.
4.2.1. 4-phenyl-1-((trimethylsilyl)methyl)-1H-1,2,3-triazole (3aa)
a All the reactions were carried out in the presence of 0.30 mmol of 1, 1.0
equiv of 2 and 10 mol% Cu2O at 80 °C under an air atmosphere.
b Isolated yield.
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 6 :
1). Yield = 97%. White solid, mp 85–88 °C. 1H NMR (600 MHz,
CDCl3) δ 7.83 (dd, J = 7.5, 0.7 Hz, 2H), 7.63 (s, 1H), 7.42 (t, J =
7.6 Hz, 2H), 7.33–7.30 (m, 1H), 3.99–3.92 (m, 2H), 0.18 (s, 9H).
13C NMR (151 MHz, CDCl3) δ 147.5, 130.8, 128.8, 127.9, 125.6,
120.2, 42.1, -2.4. IR (film) υmax: 3133, 2956, 1947, 1670, 1609,
1463, 1437, 1250, 851, 765, 693 cm-1. HRMS calc. for
C12H17N3Si (M+H)+, 232.1265; found, 232.1263.
c
The reaction was carried out in H2O (3 mL).
d The reaction was carried out under solvent free conditions.
A possible mechanism for this transformation is proposed, as
shown in Scheme 1, on the basis of the precedent literature.3,7l
Firstly, the decarboxylation of alkynyl carboxylic acid with the
assistance of a copper salt gives the alkynyl copper intermediate
A. Then the intermediate A is subjected to the CuAAC pathway,
giving rise to the formation of C-5 cuprate–triazole intermediate
C. Finally, intermediate C was quenched by proton to yield the
desired 1,2,3-triazole 3aa.
4.2.2. 1-benzyl-4-phenyl-1H-1,2,3-triazole (3ab)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 6 :
1). Yield = 87%. White solid, mp 128–133 °C.1H NMR (600
MHz, CDCl3) δ 7.82–7.75 (m, 2H), 7.66 (s, 1H), 7.45–7.33 (m,
5H), 7.31 (t, J = 7.4 Hz, 3H), 5.56 (s, 2H). 13C NMR (151 MHz,
CDCl3) δ 148.2, 134.6, 130.5, 129.1, 128.8, 128.7, 128.1, 128.0,
125.6, 119.5, 54.2. IR (film) υmax: 3446, 3142, 1645, 1607, 1552,
1494, 1452, 1208, 1046, 768, 729, 695 cm-1. HRMS calc. for
C15H13N3 (M+H)+, 236.1182; found, 236.1181.
4.2.3. ethyl 2-(4-phenyl-1H-1,2,3-triazol-1-yl)acetate (3ac)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 3 :
1). Yield = 88%. White solid, mp 95–97 °C. 1H NMR (600 MHz,
CDCl3) δ 7.92 (s, 1H), 7.84 (dd, J = 8.2, 1.1 Hz, 2H), 7.43 (dd, J
Scheme 1. Proposed mechanism.

4
Tetrahedron
= 10.7, 4.6 Hz, 2H), 7.37–7.30 (m, 1H), 5.20 (s, 2H), 4.27 (q, J
cm-1. HRMS calc. for C H BrN (M+H)+, 300.0131; found,
ACCEPTED MANUSCRIPT
14 10 3
= 7.1 Hz, 2H), 1.30 (t, J = 7.1 Hz, 3H). 13C NMR (151 MHz,
CDCl3) δ 166.2, 148.2, 130.3, 128.8, 128.2, 125.7, 120.9, 62.4,
50.9, 14.0. IR (film) υmax: 3488, 3135, 3007, 2947, 1754, 1648,
1465, 1373, 1220, 1016, 768, 693 cm-1. HRMS calc. for
C12H13N3O2 (M+H)+, 232.1081; found, 232.1082.
300.0128.
4.2.9. 3-(4-phenyl-1H-1,2,3-triazol-1-yl)phenol (3ai)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 2 :
1). Yield = 80%. White solid, mp 214–217 °C. 1H NMR (600
MHz, DMSO-d6) δ 10.15 (s, 1H), 9.27 (s, 1H), 7.96 (dd, J = 8.2,
1.1 Hz, 2H), 7.51 (dd, J = 10.7, 4.8 Hz, 2H), 7.42 (t, J = 8.0 Hz,
1H), 7.41–7.35 (m, 3H), 6.92 (ddd, J = 8.1, 2.3, 0.9 Hz, 1H). 13C
NMR (151 MHz, DMSO-d6) δ 158.6, 147.2, 137.6, 130.8, 130.3,
4.2.4. 2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethan-1-ol (3ad)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 3 :
1). Yield = 72%. White solid, mp 85–87 °C. 1H NMR (600 MHz,
CDCl3) δ 7.77 (s, 1H), 7.61 (d, J = 7.3 Hz, 2H), 7.34 (t, J = 7.3
Hz, 2H), 7.29 (t, J = 7.2 Hz, 1H), 4.45 (d, J = 4.0 Hz, 2H), 4.34–
4.14 (m, 1H), 4.10 (d, J = 3.7 Hz, 2H). 13C NMR (151 MHz,
CDCl3) δ 147.2, 130.0, 128.7, 128.1, 125.4, 121.0, 61.0, 53.0. IR
(film) υmax: 3309, 3132, 2927, 2879, 1660, 1578, 1463, 1215,
1078, 1039, 762, 696 cm-1. HRMS calc. for C10H11N3O (M+H)+,
190.0975; found, 190.0972
129.0, 128.2, 125.4, 119.6, 115.7, 110.4, 107.0. IR (film) υmax
:
3144, 1615, 1601, 1556, 1511, 1330, 1275, 1106, 765, 711, 693
cm-1. HRMS calc. for C15H13N3O (M+H)+, 238.0975; found,
238.0976.
4.2.10. 1-(3-methoxyphenyl)-4-phenyl-1H-1,2,3-triazole (3aj)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 6 :
1). Yield = 92%. White solid, mp 111–113 °C. H NMR (600
4.2.5. 1,4-diphenyl-1H-1,2,3-triazole (3ae)
1
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 8 :
1). Yield = 95%. White solid, mp 241–243 °C. 1H NMR (600
MHz, CDCl3) δ 8.20 (s, 1H), 7.96–7.85 (m, 2H), 7.80 (d, J = 7.7
Hz, 2H), 7.55 (t, J = 7.9 Hz, 2H), 7.50–7.41 (m, 3H), 7.37 (t, J =
7.4 Hz, 1H). 13C NMR (151 MHz, CDCl3) δ 148.4, 137.0, 130.2,
MHz, CDCl3) δ 8.18 (s, 1H), 7.90 (d, J = 8.1 Hz, 2H), 7.43 (dd, J
= 9.9, 4.5 Hz, 2H), 7.40 (ddd, J = 9.9, 5.8, 1.7 Hz, 2H), 7.37 –
7.32 (m, 1H), 7.29 (dd, J = 7.9, 0.8 Hz, 1H), 6.98–6.93 (m, 1H),
3.88–3.84 (m, 3H). 13C NMR (151 MHz, CDCl3) δ 160.5, 148.2,
137.9, 130.4, 130.1, 128.8, 128.3, 125.7, 117.6, 114.5, 112.2,
106.2, 55.5. IR (film) υmax: 3443, 3126, 3010, 1652, 1605, 1478,
1264, 1040, 848, 765, 690 cm-1. HRMS calc. for C15H13N3O
(M+H)+, 252.1131; found, 252.1131.
129.8, 128.9, 128.8, 128.4, 125.8, 120.5, 117.6. IR (film) υmax
:
3445, 3120, 1652, 1597, 1503, 1459, 1415, 1231, 1040, 758, 691
cm-1. HRMS calc. for C14H11N3 (M+H)+, 222.1026; found,
222.1027.
4.2.11. 1-(3-chlorophenyl)-4-phenyl-1H-1,2,3-triazole (3ak)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 5 :
1). Yield = 84%. White solid, mp 167–170 °C. 1H NMR (600
MHz, CDCl3) δ 8.19 (s, 1H), 7.93–7.88 (m, 2H), 7.85 (t, J = 1.9
Hz, 1H), 7.72 (dd, J = 8.0, 1.0 Hz, 1H), 7.51–7.42 (m, 4H), 7.39
(t, J = 7.4 Hz, 1H). 13C NMR (151 MHz, CDCl3) δ 148.6, 137.9,
135.6, 130.9, 129.9, 129.0, 128.8, 128.6, 125.9, 120.7, 118.4,
117.4. IR (film) υmax: 3444, 3098, 1651, 1590, 1480, 1453, 1286,
1157, 791, 765, 695 cm-1. HRMS calc. for C14H10ClN3 (M+H)+,
256.0636; found, 256.0635.
4.2.6. 4-phenyl-1-(p-tolyl)-1H-1,2,3-triazole (3af)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 6 :
1). Yield = 91%. White solid, mp 174–176 °C. 1H NMR (600
MHz, CDCl3) δ 8.15 (s, 1H), 7.90 (dd, J = 8.1, 1.0 Hz, 2H), 7.65
(d, J = 8.4 Hz, 2H), 7.45 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 7.4 Hz,
1H), 7.32 (d, J = 8.0 Hz, 2H), 2.42 (s, 3H). 13C NMR (151 MHz,
CDCl3) δ 148.2, 138.8, 134.7, 130.3, 130.2, 128.8, 128.3, 125.8,
120.4, 117.6, 21.1. IR (film) υmax: 3439, 2130, 1643, 1518, 1401,
1230, 1116, 1042, 816, 761, 693 cm-1. HRMS calc. for C15H13N3
(M+H)+, 236.1182; found, 236.1180.
4.2.12. 1-(3-fluorophenyl)-4-phenyl-1H-1,2,3-triazole (3al)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 2 :
1). Yield = 92%. White solid, mp 185–187 °C. 1H NMR (600
MHz, CDCl3) δ 8.20 (s, 1H), 7.91 (dd, J = 5.1, 3.2 Hz, 2H), 7.63–
7.56 (m, 2H), 7.55–7.50 (m, 1H), 7.47 (dd, J = 10.5, 4.8 Hz, 2H),
7.42–7.35 (m, 1H), 7.21–7.12 (m, 1H). 13C NMR (151 MHz,
CDCl3) δ 163.1 (d, JC-F = 248.7 Hz), 148.6, 138.2 (d, JC-F = 9.9
Hz), 131.2 (d, JC-F = 9.1 Hz), 129.9, 129.0, 128.6, 125.9, 117.4,
4.2.7. 1-(4-methoxyphenyl)-4-phenyl-1H-1,2,3-triazole (3ag)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 5 :
1
1). Yield = 91%. White solid, mp 166–169 °C. H NMR (600
MHz, CDCl3) δ 8.11 (s, 1H), 7.92–7.86 (m, 2H), 7.70–7.64 (m,
2H), 7.45 (t, J = 7.6 Hz, 2H), 7.35 (t, J = 7.4 Hz, 1H), 7.02 (d, J =
8.9 Hz, 2H), 3.86 (s, 3H). 13C NMR (151 MHz, CDCl3) δ 159.8,
148.1, 130.4, 130.3, 128.8, 128.3, 125.7, 122.1, 117.8, 114.7,
55.6. IR (film) υmax: 3450, 3120, 2961, 1649, 1551, 1457, 1238,
1036, 827, 766, 694, cm-1. HRMS calc. for C15H13N3O (M+H)+,
252.1131; found, 252.1130.
115.8 (d, JC-F = 3.3 Hz), 115.7 (d, JC-F = 21.1 Hz), 108.2 (d, JC-F
=
26.2 Hz). 19F NMR (565 MHz, CDCl3) δ -109.62. IR (film) υmax
:
3446, 3121, 1649, 1607, 1501, 1450, 1232, 916, 763, 694 cm-1.
HRMS calc. for C14H10FN3 (M+H)+, 240.0932; found, 240.0931.
4.2.8. 1-(4-bromophenyl)-4-phenyl-1H-1,2,3-triazole (3ah)
4.2.13. 4-phenyl-1-(o-tolyl)-1H-1,2,3-triazole (3am)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 4 :
1). Yield = 91%. White solid, mp 165–167 °C. 1H NMR (600
MHz, DMSO-d6) δ 9.40 (s, 1H), 8.23 (d, J = 1.7 Hz, 1H), 8.06–
8.00 (m, 1H), 7.95 (d, J = 7.8 Hz, 2H), 7.73 (d, J = 8.0 Hz, 1H),
7.61 (t, J = 8.1 Hz, 1H), 7.52 (t, J = 7.6 Hz, 2H), 7.41 (t, J = 7.2
Hz, 1H). 13C NMR (151 MHz, DMSO-d6) δ 147.6, 135.8, 132.9,
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 7 :
1). Yield = 54%. White solid, mp 199–201 °C. 1H NMR (600
MHz, CDCl3) δ 7.96 (s, 1H), 7.92 (dd, J = 8.2, 1.1 Hz, 2H), 7.48–
7.44 (m, 2H), 7.44–7.41 (m, 1H), 7.40–7.33 (m, 4H), 2.27 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 147.5, 136.4, 133.7, 131.5, 130.3,
129.9, 128.9, 128.3, 126.8, 125.9, 125.7, 121.1, 17.9. IR (film)
υmax: 3442, 3123, 2924, 1638, 1465, 1408, 1233, 1039, 761, 694
130.1, 129.1, 128.4, 125.3, 121.9, 121.4, 119.7. IR (film) υmax
:
3441, 3096, 1648, 1583, 1559, 1507, 1460, 1226, 1040, 765, 695

cm-1. HRMS calc. for C15H13N3 (M+H)+, 236.1182; found,
236.1182.
4.2.19.
(3ca)
4-(p-tolyl)-1-((trimethylsilyl)methyl)-1H-1,2,3-triazole
ACCEPTED MANUSCRIPT
4.2.14. 2-(4-phenyl-1H-1,2,3-triazol-1-yl)benzonitrile (3an)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 7 :
1). Yield = 70%. White solid, mp 110–112 ℃. H NMR (600
MHz, CDCl3) δ 7.71 (d, J = 8.2 Hz, 2H), 7.59 (s, 1H), 7.20 (d, J
= 8.0 Hz, 2H), 3.90 (s, 2H), 2.35 (s, 3H), 0.15 (s, 9H). 13C NMR
(151 MHz, CDCl3) δ 147.2, 137.5, 129.2, 127.8, 125.3, 119.8,
41.8, 21.1, -2.6. IR (film) υmax: 3442, 3136, 2954, 1909, 1659,
1558, 1453, 1250, 1216, 852, 702 cm-1. HRMS calc. for
C13H19N3Si (M+H)+, 246.1421; found, 246.1421.
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 2 :
1). Yield = 92%. White solid, mp 168–174 °C. 1H NMR (600
MHz, CDCl3) δ 8.46 (s, 1H), 7.97–7.94 (m, 1H), 7.93 (dd, J = 5.1,
3.2 Hz, 2H), 7.88 (dd, J = 7.8, 1.2 Hz, 1H), 7.82 (td, J = 7.9, 1.5
Hz, 1H), 7.61 (td, J = 7.7, 1.1 Hz, 1H), 7.48 (dd, J = 10.5, 4.8 Hz,
2H), 7.42–7.36 (m, 1H).13C NMR (151 MHz, CDCl3) δ 148.7,
138.6, 134.5, 134.4, 129.7, 129.5, 129.0, 128.8, 126.1, 125.3,
119.8, 115.8, 106.3. IR (film) υmax: 3433, 3131, 2232, 1646, 1601,
1509, 1450, 1231, 1033, 768, 689 cm-1. HRMS calc. for C15H10N4
(M+H)+, 247.0978; found, 249.0979.
1
4.2.20. 4-(4-chlorophenyl)-1-((trimethylsilyl)methyl)-1H-1,2,3-
triazole (3da)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 5 :
4.2.15. 5-bromo-2-(4-phenyl-1H-1,2,3-triazol-1-yl)benzonitrile
(3ao)
1
1). Yield = 73%. White solid, mp 108–110 ℃. H NMR (600
MHz, CDCl3) δ 7.76 (d, J = 8.6 Hz, 2H), 7.62 (s, 1H), 7.39 (d, J
= 8.6 Hz, 2H), 3.95 (s, 2H), 0.18 (s, 9H). 13C NMR (151 MHz,
CDCl3) δ 146.4, 133.6, 129.3, 129.0, 126.8, 120.2, 42.1, -2.5. IR
(film) υmax: 3448, 2957, 1654, 1482, 1401, 1245, 1089, 974, 838,
516 cm-1. HRMS calc. for C12H16ClN3Si (M+H)+, 266.0875;
found, 266.0874.
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 3 :
1). Yield = 82%. White solid, mp 199–203 °C. 1H NMR (600
MHz, CDCl3) δ 8.46 (s, 1H), 8.00 (d, J = 2.1 Hz, 1H), 7.96–7.90
(m, 3H), 7.87 (d, J = 8.7 Hz, 1H), 7.48 (t, J = 7.6 Hz, 2H), 7.41 (t,
J = 7.4 Hz, 1H). 13C NMR (151 MHz, CDCl3) δ 148.9, 137.7,
137.5, 136.7, 129.4, 129.0, 128.9, 126.4, 126.1, 122.9, 119.5,
114.6, 107.5. IR (film) υmax: 3441, 3116, 2235, 1631, 1503, 1477,
1390, 1228, 1031, 834, 767, 694 cm-1. HRMS calc. for
C15H9BrN4 (M+H)+, 325.0083; found, 325.0084.
4.2.21.
4-(1-((trimethylsilyl)methyl)-1H-1,2,3-triazol-4-
yl)benzonitrile (3ea)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 2 :
1). Yield = 46%. White solid, mp 146–149 ℃.1H NMR (600 MHz,
CDCl3) δ 8.00–7.90 (m, 2H), 7.81 (s, 1H), 7.69 (dd, J = 8.2, 2.1
Hz, 2H), 3.99 (s, 2H), 0.19 (s, 9H). 13C NMR (151 MHz, CDCl3)
δ 145.4, 135.1, 132.5, 125.8, 121.4, 118.7, 110.9, 42.1, -2.6. IR
(film) υmax: 3426, 3124, 2956, 2219, 1665, 1615, 1405, 1299,
1237, 845, 701 cm-1. HRMS calc. for C13H16N4Si (M+H)+,
257.1217; found, 257.1215.
4.2.16. 1-(naphthalen-2-yl)-4-phenyl-1H-1,2,3-triazole (3ap)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 5 :
1). Yield = 63%. White solid, mp 199–201 °C. 1H NMR (600
MHz, CDCl3) δ 8.34 (s, 1H), 8.24 (s, 1H), 8.04 (d, J = 8.7 Hz,
1H), 8.01–7.84 (m, 5H), 7.65–7.53 (m, 2H), 7.49 (t, J = 7.5 Hz,
2H), 7.39 (t, J = 7.3 Hz, 1H). 13C NMR (151 MHz, CDCl3) δ
148.5, 134.4, 133.2, 132.9, 130.2, 130.1, 128.9, 128.5, 128.3,
4.2.22. 3-(1-((trimethylsilyl)methyl)-1H-1,2,3-triazol-4-yl)phenol
128.0, 127.5, 127.0, 125.9, 118.9, 118.4, 117.7. IR (film) υmax
:
(3fa)
3440, 3121, 1643, 1600, 1480, 1445, 1255, 1090, 819, 763, 740,
692 cm-1. HRMS calc. for C18H13N3 (M+H)+, 272.1182; found,
272.1182.
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 3 :
1). Yield = 81%. White solid, mp 136–140 ℃. H NMR (600
1
4.2.17. methyl 2-(4-phenyl-1H-1,2,3-triazol-1-yl)thiophene-3-
carboxylate (3aq)
MHz, CD3OD) δ 8.45 (s, 1H), 7.33 (t, J = 7.9 Hz, 1H), 7.29–7.21
(m, 2H), 6.89 (ddd, J = 8.1, 2.4, 0.9 Hz, 1H), 4.20 (s, 2H), 0.21 (s,
9H). 13C NMR (151 MHz, MeOD) δ 159.5, 146.8, 131.5, 129.8,
124.7, 118.2, 117.8, 113.9, 44.4, -2.7. IR (film) υmax: 3028, 2954,
1696, 1622, 1588, 1472, 1414, 1371, 1281, 846, 783 cm-1. HRMS
calc. for C12H17N3OSi (M+H)+, 248.1214; found, 248.1210.
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 4 :
1). Yield = 78%. White solid, mp 147–149 °C. 1H NMR (600
MHz, CDCl3) δ 8.67 (s, 1H), 7.92 (dd, J = 8.2, 1.1 Hz, 2H), 7.63–
7.59 (m, 1H), 7.59–7.55 (m, 1H), 7.44 (t, J = 7.7 Hz, 2H), 7.37 –
7.32 (m, 1H), 3.85 (t, J = 1.3 Hz, 3H). 13C NMR (151 MHz,
CDCl3) δ 160.6, 146.9, 138.3, 131.0, 130.1, 128.8, 128.2, 126.4,
125.8, 122.3, 121.3, 52.5. IR (film) υmax: 3402, 3111, 1708, 1560,
1473, 1437, 1314, 1190, 796, 780, 695 cm-1. HRMS calc. for
C14H11N3O2S (M+H)+, 286.0645; found, 286.0643.
4.2.23.
4-(m-tolyl)-1-((trimethylsilyl)methyl)-1H-1,2,3-triazole
(3ga)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 7 :
1). Yield = 78%. White solid, mp 78–80 ℃. 1H NMR (600 MHz,
CDCl3) δ 7.68 (s, 1H), 7.62 (s, 1H), 7.59 (d, J = 7.7 Hz, 1H), 7.29
(t, J = 7.6 Hz, 1H), 7.13 (d, J = 7.5 Hz, 1H), 3.93 (s, 2H), 2.38 (s,
3H), 0.16 (s, 9H). 13C NMR (151 MHz, CDCl3) δ 147.4, 138.3,
130.6, 128.59, 128.57, 126.1, 122.6, 120.1, 41.9, 21.3, -2.6. IR
(film) υmax: 3445, 2955, 1616, 1558, 1493, 1249, 1221, 842, 794,
699 cm-1. HRMS calc. for C13H19N3Si (M+H)+, 246.1421; found,
246.1418.
4.2.18. 4-(4-methoxyphenyl)-1-((trimethylsilyl)methyl)-1H-1,2,3-
triazole (3ba)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 6 :
1
1). Yield = 88%. White solid, mp 106–108 ℃. H NMR (600
MHz, CDCl3) δ 7.75 (d, J = 8.8 Hz, 2H), 7.55 (s, 1H), 6.95 (d, J
= 8.8 Hz, 2H), 3.93 (s, 2H), 3.84 (s, 3H), 0.17 (s, 9H). 13C NMR
(151 MHz, CDCl3) δ 159.4, 147.3, 126.8, 123.5, 119.4, 114.1,
55.3, 42.0, -2.5. IR (film) υmax: 3132, 2955, 1615, 1558, 1498,
1409, 1249, 1030, 837, 799, 702 cm-1. HRMS calc. for
C13H19N3OSi (M+H)+, 262.1370; found, 262.1367.
4.2.24. 4-(3-fluorophenyl)-1-((trimethylsilyl)methyl)-1H-1,2,3-
triazole (3ha)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 6 :

6
Tetrahedron
1
1). Yield = 74%. White solid, mp 107–111 ℃. H NMR (600
7.44–7.36 (m, 1H), 2.82–2.74 (m, 2H), 1.79–1.68 (m, 2H), 1.41–
1.34 (m, 4H), 0.91 (t, J = 7.1 Hz, 3H). 13C NMR (151 MHz,
CDCl3) δ 149.1, 137.2, 129.6, 128.3, 120.3, 118.7, 31.4, 29.0,
25.6, 22.4, 13.9. IR (film) υmax: 3139, 2957, 2932, 1599, 1502,
1464, 1343, 1228, 1043, 756, 690 cm-1. HRMS calc. for C13H17N3
(M+H)+, 216.1495; found, 216.1491.
ACCEPTED MANUSCRIPT
MHz, CDCl3) δ 7.64 (s, 1H), 7.61–7.57 (m, 1H), 7.55 (ddd, J =
10.0, 2.4, 1.6 Hz, 1H), 7.38 (td, J = 8.0, 6.0 Hz, 1H), 7.04–6.97
(m, 1H), 3.96 (s, 2H), 0.18 (s, 9H). 13C NMR (151 MHz, CDCl3)
δ 163.1 (d, JC-F = 245.4 Hz), 146.4 (d, JC-F = 2.7 Hz), 133.0 (d, JC-
= 8.5 Hz), 130.3 (d, JC-F = 8.5 Hz), 121.1 (d, JC-F = 2.8 Hz),
F
120.5 , 114.7 (d, JC-F = 21.2 Hz), 112.5 (d, JC-F = 22.9 Hz), 42.1, -
4.2.30. 4-cyclopropyl-1-phenyl-1H-1,2,3-triazole (3qe)
2.5. 19F NMR (565 MHz, CDCl3) δ -112.81. IR (film) υmax
:
3135, 2958, 1621, 1588, 1444, 1251, 1225, 1000, 851, 784 cm-1.
HRMS calc. for C12H16FN3Si (M+H)+, 250.1170; found,
250.1168.
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 5 :
1). Yield = 41%. White solid, mp 75–78 ℃. 1H NMR (600 MHz,
CDCl3) δ 7.70 (dd, J = 9.2, 1.4 Hz, 3H), 7.49 (t, J = 7.9 Hz, 2H),
7.43–7.38 (m, 1H), 2.07–1.98 (m, 1H), 1.03–0.98 (m, 2H), 0.95–
0.91 (m, 2H). 13C NMR (151 MHz, CDCl3) δ 150.9, 137.1, 129.6,
128.4, 120.3, 117.8, 7.8, 6.6. IR (film) υmax: 3495, 3137, 1636,
1568, 1502, 1462, 1231, 1051, 757, 692 cm-1. HRMS calc. for
C11H11N3 (M+H)+, 186.1026; found, 186.1025.
4.2.25.
4-(3-nitrophenyl)-1-((trimethylsilyl)methyl)-1H-1,2,3-
triazole (3ia)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 3 :
1
1). Yield = 77%. White solid, mp 136–139 ℃. H NMR (600
MHz, CDCl3) δ 8.64–8.57 (m, 1H), 8.28–8.21 (m, 1H), 8.16 (ddd,
J = 8.2, 2.2, 0.9 Hz, 1H), 7.82 (s, 1H), 7.61 (t, J = 8.0 Hz, 1H),
4.01 (s, 2H), 0.20 (s, 9H). 13C NMR (151 MHz, CDCl3) δ 148.5,
145.2, 132.6, 131.3, 129.8, 122.4, 121.1, 120.2, 42.3, -2.5. IR
(film) υmax: 3124, 3094, 2960, 2918, 1669, 1525, 1460, 1348,
1251, 847, 758 cm-1. HRMS calc. for C12H16N4O2Si (M+H)+,
277.1115; found, 277.1112.
Acknowledgments
This research was supported by the National Natural Science
Foundation of China (No. 21662021) and the Science and
Technology Planning Project of Yunnan Province (Nos.
2017FB016 and 2018FA047).
4.2.26. 4-(2-methoxyphenyl)-1-((trimethylsilyl)methyl)-1H-1,2,3-
triazole (3ja)
References and notes
1. (a) Kolb, H. C.; Sharpless, K. B. Drug Discovery Today 2003, 8,
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Sharpless, K. B.; Fokin, V. V. Angew. Chem., Int. Ed. 2004, 43,
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Chem. Sci. 2016, 7, 6298.
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 7 :
1). Yield = 88%. White solid, mp 62–63 ℃. 1H NMR (600 MHz,
CDCl3) δ 8.34 (dd, J = 7.7, 1.7 Hz, 1H), 7.92 (s, 1H), 7.32–7.27
(m, 1H), 7.07 (t, J = 7.5 Hz, 1H), 6.96 (d, J = 8.3 Hz, 1H), 3.94 (s,
2H), 3.92 (s, 3H), 0.17 (s, 9H). 13C NMR (151 MHz, CDCl3) δ
155.4, 142.7, 128.6, 127.4, 123.8, 120.9, 119.6, 110.7, 55.3, 41.7,
-2.5. IR (film) υmax: 2961, 2911, 2842, 1605, 1546, 1489, 1442,
1249, 1023, 856, 761 cm-1. HRMS calc. for C13H19N3OSi (M+H)+,
262.1370; found, 262.1369.
4.2.27. 1-phenyl-1H-1,2,3-triazole (3ne)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 6 :
1). Yield = 57%. White solid, mp 49–53 ℃. 1H NMR (600 MHz,
CDCl3) δ 8.02 (d, J = 1.0 Hz, 1H), 7.85 (d, J = 2.9 Hz, 1H), 7.75
(dd, J = 5.7, 2.3 Hz, 2H), 7.53 (dd, J = 9.8, 5.5 Hz, 2H), 7.48–
7.42 (m, 1H). 13C NMR (151 MHz, CDCl3) δ 136.9, 134.4, 129.7,
128.7, 121.7, 120.6. IR (film) υmax: 3147, 2921, 1595, 1502, 1319,
1229, 1096, 1036, 762, 686 cm-1. HRMS calc. for C8H7N3
(M+H)+, 146.0713; found, 146.0711.
2. (a) Agalave, S. G.; Maujan, S. R.; Pore, V. S. Chem.–Asian J.
2011, 6, 2696; (b) Wei, F.; Wang, W.; Ma, Y.; Tung, C.-H.; Xu, Z.
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3. (a) Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B.
Angew. Chem., Int. Ed. 2002, 41, 2596; (b) Tornoe, C. W.;
Christensen, C.; Meldal, M. J. Org. Chem. 2002, 67, 3057; (c)
Meldal, M.; Tornøe, C. W. Chem. Rev. 2008, 108, 2952; (d) Hein,
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4. For recent reviews on decarboxylation, see: (a) Baudoin, O.
Angew. Chem., Int. Ed. 2007, 46, 1373; (b) Gooßen, L. J.;
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5. For selected papers, see: (a) Myers, A. G.; Tanaka, D.; Mannion,
M. R. J. Am. Chem. Soc. 2002, 124, 11250; (b) Gooßen, L. J.;
Deng, G.; Levy, L. M. Science 2006, 313, 662; (c) Fang, P.; Li,
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4.2.28. 1-phenyl-4-propyl-1H-1,2,3-triazole (3oe)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 7 :
1). Yield = 88%. White turbid liquid. 1H NMR (600 MHz, CDCl3)
δ 7.81–7.65 (m, 3H), 7.50 (t, J = 7.9 Hz, 2H), 7.41 (t, J = 7.4 Hz,
1H), 2.78 (t, J = 7.6 Hz, 2H), 1.81–1.72 (m, 2H), 1.01 (t, J = 7.4
Hz, 3H). 13C NMR (151 MHz, CDCl3) δ 148.9, 137.2, 129.6,
128.3, 120.3, 118.8, 27.6, 22.6, 13.7. IR (film) υmax: 3134, 2958,
1599, 1556, 1506, 1464, 1228, 1047, 987, 756, 687 cm-1. HRMS
calc. for C11H13N3 (M+H)+, 188.1182; found, 188.1178.
4.2.29. 4-pentyl-1-phenyl-1H-1,2,3-triazole (3pe)
This compound was prepared by the general procedures. Purified
by column chromatography (petroleum ether : ethyl acetate = 7 :
1). Yield = 91%. White solid, mp 41–43 ℃. 1H NMR (600 MHz,
CDCl3) δ 7.72 (ddd, J = 4.2, 3.5, 2.4 Hz, 3H), 7.54–7.45 (m, 2H),

Ahneman, D. T.; Chu, L.; Terrett, J. A.; DoyAle, CA.CG.E; MPaTcMEillDan, MANUSCRIPT
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