Base-mediated reaction of vinyl bromides with aryl azides: One-pot synthesis of 1,5-disubstituted 1,2,3-triazoles

Article abstract of DOI:10.1016/j.tetlet.2014.03.029

A one-pot base-mediated reaction of azides and β- or α-vinyl bromides has been reported. The effects of bases and solvents have been investigated in the process. A variety of 1,5-disubstituted triazoles were prepared in low to good yields. Further studies reveal that the corresponding alkynes were produced as intermediates via elimination reaction. Under the same reaction conditions, the reactions of alkyl alkynes with phenyl azide would give 1,5-disubstituted 1,2,3-triazoles.

Full text of DOI:10.1016/j.tetlet.2014.03.029

Accepted Manuscript
Base-mediated reaction of vinyl bromides with aryl azides: one-pot synthesis of
1,5-disubstituted 1,2,3-triazoles
Luyong Wu, Yuxue Chen, Jianheng Luo, Qi Sun, Mingsheng Peng, Qiang Lin
PII:
S0040-4039(14)00427-4
DOI:
http://dx.doi.org/10.1016/j.tetlet.2014.03.029
TETL 44351
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
1 December 2013
22 February 2014
6 March 2014
Please cite this article as: Wu, L., Chen, Y., Luo, J., Sun, Q., Peng, M., Lin, Q., Base-mediated reaction of vinyl
bromides with aryl azides: one-pot synthesis of 1,5-disubstituted 1,2,3-triazoles, Tetrahedron Letters (2014), doi:
http://dx.doi.org/10.1016/j.tetlet.2014.03.029
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Base-Mediated Reaction of Vinyl Bromides
with Aryl Azides: One-Pot Synthesis of 1,5-
Disubstituted 1,2,3-Triazoles
Leave this area blank for abstract info.
Luyong Wu, Yuxue Chen, Jianheng Luo, Qi Sun, Mingshen
Qiang Lin
R2
N
N
KOtBu
DMF or THF
Br
N
R2N3
R1
R1
23 examples
30 - 96% yields
R1 = alkyl, aryl
R2 = aryl

Tetrahedron Letters
1
Tetrahedron Letters
jo u rn al h ome p ag e : w ww .e lse vie r .c om
Base-Mediated Reaction of Vinyl Bromides with Aryl Azides: One-Pot Synthesis of
1,5-Disubstituted 1,2,3-Triazoles
Luyong Wua, b, Yuxue Chenb, Jianheng Luoa, Qi Suna, Mingsheng Penga, b and Qiang Lina, b,
∗
aCollege of Chemistry and Chemical Engineering, Hainan Normal University, No.99, Longkun South Road, Haikou 571158, P. R. China
bKey Laboratory of Tropical Medicinal Plant Chemistry of Ministry of Education, Hainan Normal University, No.99, Longkun South Road, Haikou 571158, P. R.
China
ARTICLE INFO
ABSTRACT
Article history:
Received
A one-pot base-mediated reaction of azides and β- or α-vinyl bromides has been reported. The
effects of bases and solvents have been investigated in the process. A variety of 1,5-disubstituted
triazoles were prepared in low to good yields. Further studies reveal that the corresponding
alkynes were produced as the intermediates via elimination reaction. Under the same reaction
conditions, the reactions of alkyl alkynes with phenyl azide would give 1,5-disubstituted 1,2,3-
triazoles.
Received in revised form
Accepted
Available online
Keywords:
1,2,3-Triazole
Vinyl bromide
Azide
2009 Elsevier Ltd. All rights reserved.
KOtBu
One-pot Reaction
1. Introduction
Vinyl halides are important intermediates in organic synthetic
chemistry7 and can be acquired handily from dihalogenoalkanes,
alkenes or other structures.7a,8 Elimination reaction of vinyl
The 1,2,3-triazole is an important structural motif found in
many biologically active compounds and material industries.1 Its
extensive applications stimulated more and more interests to
develop synthetic methodologies of the 1,2,3-triazole formation
over the past decades.2 Among numerous synthetic approaches,
one of the most important and efficient methods to form the
triazole ring system is the Huisgen cycloaddition reaction
between azides and unsaturated compounds with multi carbon-
carbon bonds (e.g. alkynes, alkenes).3 In many reports
concerning Huisgen cycloaddition reaction, two isomers were
formed when unsymmetric alkynes or alkenes without activated
functional groups were used. This unbearable disadvantage
limited the application of the Huisgen cycloaddition reaction.
About ten years ago, the Cu-catalyzed cycloaddition from
organic azides and terminal alkynes to form 1,4-regioisomers (as
sole product) of 1,2,3-triazoles was disclosed by Tornøe and
Sharpless et al. 4 Stimulated by the reports, other regioselective
and reliable 1,2,3-triazole-forming processes have been explored
from azides and alkynes, especially terminal alkynes.5
halides, one of most classical reactions to synthesize alkynes
(including terminal alkynes), has received intensively attentions.9
Up to now, a few papers have studied the reactions of vinyl
bromides with sodium azide or trimethylsilyl azide to generate
1H-1,2,3-triazoles under transition metal catalytic conditions. 10 It
is indicated that these reactions underwent cycloaddition-
elimination processes. However, to the best of our knowledge,
one-pot synthesis of 1,2,3-triazoles without transition metal
catalysis from vinyl bromides and aryl- or alkyl- azides has rarely
been reported. In addition, the nucleophilic attack at organic
azides by alkynyl anions which are in situ generated through
further deprotonation of the intermediates that are formed from
the dehydrohalogenation of vinyl halides would enable us to
develop a new approach to synthesize 1,5-disubstituted 1,2,3-
triazoles.11 (Scheme 1).
R2
N
Br
base
N
R2N3
N
R1
one-pot
R1
Scheme 1
To some extent, terminal alkynes are more expensive and less
easily available intermediates. Therefore, the in situ generations
of terminal alkynes from desilylation of TMS-alkynes,
decarboxylation of alkynoic acids or Seyferth-Gilbert
Homologation of aldehydes have been applied in the synthesis of
2. Results and discussions
To confirm the viability of the envisioned one-pot protocol,
our initial study chose the reaction of (E)-β-phenyl vinyl bromide
(1a) with phenyl azide (2a) as the model reaction, and the results
1,2,3-triazoles.6
———
∗ Corresponding author. Tel.: +86-898-6588-9422; fax: +86-898-6588-9422; e-mail: linqiang@hainnu.edu.cn

2
Tetrahedron Letters
were summarized in Table 1. Considering that the strong bases
a Unless otherwise indicated, all reactions were performed with 1a (0.5 mmol),
2a (0.5 mmol) and 2.0 equivalent base (1 mmol) in solvent (1 mL) under an
argon atmosphere at ambient temperature.
were necessary in the elimination of vinyl halides and the
formation of alkynyl anions, we firstly carried out the cascade
reaction with 2.0 equivalent KOtBu as the base in DMSO. As
expected, the desired product 3a was isolated and identified by
1H NMR and 13C NMR spectra, however, only a moderate yield
was obtained (Table 1, entry 1). In the process, the reaction
mixture turned black and the temperature increased sharply when
KOtBu was added. On the other hand, several unknown
byproducts were observed by TLC. The dissatisfactory results
were probably related to the strong alkalinity and the high
solubility of KOtBu in DMSO. Employment of KOH powder as
the base with or without the presence of the phase-transfer
catalyst was less effective (Table 1, entry 2-4). When the base
was switched to KH or sodium bis(trimethylsilyl)amide in
DMSO, 3a was furnished in low yields (Table 1, entries 5 and 6).
Subsequently, we screened other solvents for the reactions of 1a
with 2a, and found that the best results were obtained when the
reactions were performed in DMF or THF as the solvent in the
presence of KOtBu (Table 1, entries 10 and 13). Theoretically,
1.0 equivalent of KOtBu is necessary to promote the elimination
reaction of arylvinyl bromide, and the catalytical amount of
KOtBu is sufficient to promote the nucleophilic attack at phenyl
azide by the intermediate (phenylacetylene).11c However, in our
experiments, the decreasing yields were observed when the
amount of KOtBu was reduced to 1.5 equivalent (Table 1, entries
17 and 18). When toluene, tert-butanol and ethyl nitrile as
solvents were used, no product was monitored. Then, NaOtBu
was attempted and very low yield was obtained (Table 1, entry
16). Foregoing results confirmed that KOtBu-mediated one-pot
reaction of (E)-β-phenyl vinyl bromide with phenyl azide could
be efficiently applied in the synthesis of 1,5-diphenyl 1,2,3-
triazole.
b Isolated yield.
c 10 mol% phase-transfer catalyst was used.
After optimizing the elimination-cyclization reaction of (E)-β-
phenyl vinyl bromide with phenyl azide, we attempted to employ
similar reaction conditions to synthesize 1,5-diphenyl 1,2,3-
triazole from α-phenyl vinyl bromide and phenyl azide; and the
results were summarized in Table 2. In general, compared to (E)-
β-phenyl vinyl bromide, α-phenyl vinyl bromide exhibited
different reaction activity in this cascade approach. When the
reactions were performed in the presence of KOtBu, the
temperature of reaction mixtures rose sharply, and the product
was afforded in 40-69% yield along with some unidentified
byproducts (Table 2, entries 1, 7 and 13 ). Addition of KOtBu to
Table 2. Conditions screening of reaction of α-phenyl vinyl bromide with
phenyl azidea
Ph
Ph
Br
N
base, solvent
N
PhN3
N
Ph
2a
1b
3a
Entry
Solvent
DMF
Base
Yield(%)b
1
2
KOtBu
68
48
66d
83
84
69
51
72
67
68
n.d.
6
DMF
KOH (4.0eq)/ Bu4N+·Br-
KOtBu
3
DMF
4
DMF
KH
5
DMF
(Me3Si)2NNa
KOH (4.0eq)
KOtBu
Table 1. Conditions screening of reaction of (E)-β-phenyl vinyl bromide with
phenyl azidea
6
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
THF
7
Ph
8
KOH (4.0eq)/ Bu4N+·Br-
KH
N
base, solvent
N
Br
PhN3
N
Ph
9
Ph
1a
2a
3a
10
11
12
13
14
15
(Me3Si)2NNa
KOH aq. (4.0eq)
KOH (4.0eq)
KOtBu
Entry
1
Solvent
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
Base
Yield(%)b
62
KOtBu
2
KOH (4.0 equiv.)
KOH/ Bu4N+·Br-
47
THF
40
9
3
50c
58c
11
THF
KH
4
KOH (4.0 equiv.) / Bu4N+·Br-
THF
(Me3Si)2NNa
90
5
KH
(Me3Si)2NNa
KOH
a Unless otherwise indicated, all reactions were performed with 1b (0.5 mmol),
2a (0.5 mmol) and base (1 mmol) in solvents (1 mL) under an argon
atmosphere at ambient temperature.
b Isolated yield. c 10 mol% phase-transfer catalyst was used.
d The reaction was performed at 0 ℃.
6
22
7
23
8
DMF
KOH/ Bu4N+·Br-
KOH (4.0 equiv.)/ Bu4N+·Br-
KOtBu
41c
51c
89
a solution of 1b and 2a in DMF under ice-cold condition gave 3a
in a similar yield (Table 2, entry 3). When KOH powder was
employed in DMSO, slightly high yields were given (Table 2,
entries 6 and 8). When saturated aqueous solution of KOH was
used, no product was monitored on TLC (Table 2, entry 11). The
employment of sodium bis(trimethylsilyl)amide as the base in
THF or DMF improved the yields up to 84-90% (Table 2, entries
5 and 15). KH was tested in the reaction and the product was
isolated in poor to good yield (Table 2, entries 4, 9 and 14).
9
DMF
10
11
12
13
14
15
16
17
18
DMF
DMF
KH
78
DMF
(Me3Si)2NNa
KOtBu
79
THF
88
THF
KH
trace
81
THF
(Me3Si)2NNa
NaOtBu
When the mixture of phenyl azide and (E)-β-phenyl vinyl
bromide or α-phenyl vinyl bromide was heated at 80℃for 24h in
the presence of K2CO3 in DMSO, only a trace amount of triazole
was observed as a mixture of geometrical isomers accompanied
by starting materials. The results would indicate that the thermal
cycloaddition of vinyl bromide with phenyl azide takes place
DMF
14
DMF
KOtBu (1.5 equiv.)
KOtBu (1.5 equiv.)
71
THF
68

Tetrahedron Letters
3
very slowly, and this base-mediated reaction is different from
Huigen cycloaddion reaction.
The efficient one-pot protocol was further extended to the
reactions of other (E)-β-aryl vinyl bromides with aryl azides to
synthesize 1,5-disubstituted 1,2,3-triazoles. The obtained results
were summarized in Table 3. Firstly, various substituted phenyl
azides 2a-2l were treated with 1a under the optimized conditions.
In general, electron-withdrawing or electron-donating substituted
groups have less influence on the reactions and good to excellent
yields were given (Table 3, entries 1-10 and 12) with the
exception of 2k in which some unknown yellowish byproduct
was isolated (Table 3, entry 11). Interestingly, ortho substituents
of azides showed little steric hindrance in the reaction (Table 3,
Although sodium bis(trimethylsilyl)amide and KH could
promote the reaction of vinyl bromide with phenyl azide in good
yields, considering their high prices, our further studies were
performed with KOtBu as the base. To demonstrate the efficiency
of KOtBu-mediated one-pot reaction of phenyl vinyl halide with
phenyl azide, we examined the transformations from phenyl
azide and (E)-β-phenyl vinyl chloride or (Z)-β-phenyl vinyl
bromide under the optimized condition, and the corresponding
product was given in high yields (Scheme 2).
entries
6
and 9). Meanwhile, 3-azidopyridine and 1-
Ph
N
KOtBu, DMF
N
azidonaphthaline were also effective to provide the desired
products in good yields (Table 3, entries 13 and 14). Other (E)-β-
aryl vinyl bromides were also employed in the reaction, and gave
corresponding adducts with considerable yields (Table 3, entries
15-20). When the substituted group was a electron-donating
group, the yield decreased to 54% (Table 3, entry 19).
Cl
N
PhN3
Ph
Ph
r.t., 89%
Ph
Ph
N
KOtBu, DMF
N
N
PhN3
r.t., 91%
Br
Ph
Scheme 2
Table 3. One-pot synthesis of 1,5-diaryl 1,2,3-triazoles from (E)-β-aryl vinyl bromides and aryl azides
R2
N
KOtBu
N
N
Br
R2N3
R1
DMF or THF
R1
1
2
3
Entry
1
R1
2
R2
Product
3a
3b
3c
Yield(%)b
87
1
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1c
1d
1e
1e
1f
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
2a
2b
2c
2d
2e
2f
C6H5
2
p-BrC6H4
88
3
p-CH3C6H4
p-ClC6H4
82
4
3d
3e
88c
82
5
m-CH3C6H4
o-CH3C6H4
p-CH3OC6H4
m-CF3C6H4
o-ClC6H4
6
3f
77
7
2g
2h
2i
3g
3h
3i
85
8
96
9
94
10
11
12
13
14
15
16
17
18
19
20
2j
m-ClC6H4
p-O2NC6H4
3j
92c
37
2k
3k
3l
2l
2m
2n
2a
2a
2a
2c
p-Et2NCOC6H4
1-naphthyl
3-pyridyl
C6H5
80c
82
3m
3n
3o
3p
3q
3r
77
p-CH3C6H4
o-CH3C6H4
p-ClC6H4
86
C6H5
79
C6H5
79c
77
p-ClC6H4
p-CH3C6H4
C6H5
p-CH3OC6H4
o-CH3C6H4
2a
2d
3s
54
1d
p-ClC6H4
3t
86
a Unless otherwise indicated, all reactions were performed with 1 (1.0 mmol), 2 (1.0 mmol) and KOtBu (2 mmol) in DMF (2 mL) under an argon atmosphere.
b Isolated yield.
c THF was used as the solvent.
Subsequently, we turned our attention to the reaction of alkyl
azides with (E)-β-phenyl vinyl bromide. Different from the
results of the methodologies concerning the nucleophilic attack at
azides by magnesium acetylides,11a,12 n-octyl azide, cyclohexyl
azide and benzyl azide failed to provide the expected products
when reacting with phenyl azide in the presence of KOtBu in
DMF. After quenching the reactions, phenyl acetylene was
monitored by GC/MS, which indicated that the initial
dehydrohalogenation of (E)-β-phenyl vinyl bromide was
successful. However, the existence of n-octyl azide or cyclohexyl
azide manifested that the nucleophilic attack of phenylacetylene
was almost unsuccessful. When benzylic azide was used,
phenylacetylene and phenylaldehyde were observed in GC/MS
after quenching the reaction. Further experiment indicated

4
Tetrahedron Letters
phenylaldehyde was generated from benzylic azide via strong
halide with aryl azide was outlined in Scheme 5.
Dehydrohalogenation of vinyl halide generates an terminal
alkyne which further transforms to an alkynyl anion through the
base-mediated deprotonation. Subsequently, nucleophilic attack
of alkynyl anion to aryl azide affords a triazenide intermediate.
Based on intramolecular cyclization, 1,5-disubstituted-1,2,3-
triazolyl anion is formed. Finally, the product is afforded after the
triazolyl anion is protonated.
base-mediated denitrogenation. Considering the acidity of
benzylic H-atom, we proposed the hypothetical mechanism as
shown in Scheme 3.
tBuOK
- N2
N
N
N
N
N
N
3. Conclusion
CHO
H2O
In summary, a base-mediated reaction of vinyl bromides with
azides was investigated and a methodology for the synthesis of
1,5-disubstituted 1,2,3-triazoles was presented. These studies
point out the importance of bases and solvents in the one-pot
multistep reaction. Meanwhile, the reactions of aryl vinyl
bromides and aryl azides tend to give better results.
N
Scheme 3
Furthermore, the reactions of phenyl azide with methyl vinyl
bromides (2-bromo prop-1-ene and 1-bromo prop-1-ene) were
tested and the desired triazole 3u was isolated in the low yield
(30% and 35%, respectively) (Scheme 4a). The mixture of 1-
bromo oct-1-ene and 2-bromo oct-1-ene (1:1) was also
transformed into the triazole 3v in the yield of 36% by reacting
with phenyl azide under the optimized condition (Scheme 4b).
The results indicated alkyl acetylenes could be suitable substrates
to react with phenyl azide under the current condition. Then, the
reaction of phenyl azide with 1-octyne or 2,2-dimethyl-1-butyne
was carried out and gave moderate yields (Scheme 4c).
Acknowledgments
This work was supported by the Natural Science Foundation
(NSF-21362008) and “the scientific research starting foundation
for youth Scholars” of Hainan Normal University. We are
grateful to our colleagues in Key Laboratory of Tropical
Medicinal Plant Chemistry of Ministry of Education of Hainan
Normal University for providing analytic services. The authors
are grateful to Yuhe Chen from Asian Institute of Technology for
his assistance in language.
Ph
N
KOtBu
DMF
Br
N
a)
Ph
+
N3
N
References and notes
H3C
3u (35%)
Ph
1.
(a) Fan, W.-Q.; Kartritzky, A. R. In Comprehensive Heterocyclic
ChemistryⅡ; Katritzky, A. R., Rees, C. W., Scriven, E. F. V.,
Eds.; Elsevier Science: Oxford, 1996; Vol. 4, pp 1–126; (b)
Whiting, M.; Muldoon, J.; Lin, Y.-C.; Silverman, S. M.;
N
KOtBu
DMF
N
Br
+
Ph N3
N
Lindstrom, W.; Olson, A. J.; Kolb, H. C.; Finn, M. G.; Sharpless,
K. B.; Elder, J. H.; Fokin, V. V. Angew. Chem. Int. Ed. 2006, 45,
1435-1439; (c) Lewis, W. G.; Green, L. G.; Grynszpan, F.; Radic,
Z.; Carlier, P. R.; Taylor, P.; Finn, M. G.; Sharpless, K. B. Angew.
Chem. Int. Ed. 2002, 41, 1053-1057; (d) Tron, G. C.; Pirali, T.;
Billington, R. A.; Canonico, P. L.; Sorba, G.; Genazzani, A. A.
Medicinal Research Reviews 2008, 28, 278-308.
H3C
3u (30%)
Ph
b)
Br
N
KOtBu
DMF
N
Br
+
Ph N3
N
Hex
Hex
( 1
Hex
1 )
:
2. (a) Krivopalov, V. P.; Shkurko, O. P. Russ. Chem. Rev. 2005, 74,
339-379; (b) Tome, A. C. In 1,2,3-triazoles. In Science of
Synthesis; Stor, R.; Gilchrist, T., Eds.; Thieme: New York, 2004;
Vol. 13, pp 415-601.
3v 36%
c)
N
Ph
KOtBu
DMF
N
3. Huisgen, R. 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.
Wiley, New York, 1984 , vol. 1, pp 1-176.
N
Ph N3
+
H
R
4. (a) Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B.
Angew. Chem., Int. Ed. 2002, 41, 2596-2599; (b) Tornøe, C. W.;
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H. H. Y.; Williams, I. D.; Sharpless, K. B.; Fokin, V. V.; Jia, G. J.
Am. Chem. Soc. 2005, 127, 15998-15999; (b) Kamijo, S.; Jin, T.;
Huo, Z.; Yamamoto, Y. J. Am. Chem. Soc. 2003, 125, 7786-7787;
(c) Wu, Y.-M.; Deng, J.; Li, Y.; Chen, Q.-Y. Synthesis 2005,
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Lett. 2009, 11, 3024-3027; (e) Baskin, J. M.; Prescher, J. A.;
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Codelli, J. A.; Bertozzi, C. R. PNAS 2007, 104, 16793-16797; (f)
Kwok, S. W.; Fotsing, J. R.; Fraser, R. J.; Rodinov, V. O.; Fokin,
V. V. Org. Lett. 2010, 12, 4217-4219; (g) Krasinski, A.; Fokin, V.
V.; Sharpless, K. B.; Org. Lett. 2004, 6, 1237-1240; (h) Meng, X.;
Xu, X.; Gao, T.; Chen, B. Eur. J. Org. Chem. 2010, 5409-5414.
6. For some recent selected examples, see: (a) Kolarovič, A.;
Schnürch, M.; Mihovilovic, M. D. J. Org. Chem., 2011, 76, 2613-
2618; (b) Luvino, D.; Amalric, C.; Smietana, M.; Vasseur, J.-J.
Synlett, 2007, 3037-3041; (c) Cuevas, F.; Oliva, A. I.; Pericàs, M.
A. Synlett, 2010, 1873-1877; (d) Friscourt, F.; Boons, G.-J. Org.
Lett. 2010, 12, 4936-4939; (e) Kamijo. S.; Jin, T.; Yamamoto, Y.
Tetrahedron Letters, 2004, 45, 689-691. (f) Wu, L.; Chen, Y.;
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1529-1533.
R
3v, R = Hex, 43%
3w, R = tert-Bu, 45%
Scheme 4
On the basis of the above results and literature precedents, a
plausible pathway for the base-mediated one-pot reaction of vinyl
Scheme 5. Plausible Pathway of base-mediated reaction of
vinyl halide with aryl azide
B
X
B
R
H
R
R
-HX
X = Cl, Br
ArN3
R
R
R
HB
N
N
N
N
N
N
N
N
N
Ar
Ar
Ar

Tetrahedron Letters
5
7. (a) Stanforth, S. P. In Comprehensive Organic Functional Group
Kwok, S. W.; Fotsing, J. R.; Fraser, R. J.; Rodinov, V. O.; Fokin,
Transformations II; Katritzky, A. R., Taylor, R. J. K., Eds.;
Elsevier: Oxford, 2005; Vol. 2, p 561; (b) Tsuji, J. In Reactions of
Organic Halides and Pseudohalides,Transition Metal Reagents
and Catalysts: InnoVations in Organic Synthesis; Wiley: New
York, 2000; pp 27-108.
V. V. Org. Lett. 2010, 12, 4217-4219; (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, 8923-8930; (e) Smith, C. D.;
Greaney, M. F. Org. Lett., 2013, 15, 4826–4829; (f) Kayet, A.;
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Supplementary Material
Supplementary material that may be helpful in the review
process should be prepared and provided as a separate electronic
file. That file can then be transformed into PDF format and
submitted along with the manuscript and graphic files to the
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6
Tetrahedron Letters
Scheme 1. Base-Promoted Reaction of Vinyl Bromides with
Azides
Scheme 2. Reaction of Phenyl Azied with (E)-β-Phenyl Vinyl
Chloride or (Z)-β-Phenyl Vinyl Bromide
Scheme 3. Plausible Mechanism of Base-mediated
Denitrogenation in Benzylic Azide
Scheme 4. Reactions of phenyl azide with alkyl vinyl bromides
or alkyl acetylenes