Copper(I)-catalyzed aerobic oxidative azide-alkene cyclo-addition: An efficient synthesis of substituted 1,2,3-triazoles

Article abstract of DOI:10.1002/adsc.201300344

A novel, copper(I)-promoted azide-alkene aerobic oxidative cycloaddition protocol was devel-oped for the regioselective synthesis of 1,4-disubsti-tuted/ 1,4,5-trisubstituted 1,2,3-triazoles by using azides and electron-deficient olefins under an oxygen atmosphere.

Full text of DOI:10.1002/adsc.201300344

FULL PAPERS
DOI: 10.1002/adsc.201300344
Copper(I)-Catalyzed Aerobic Oxidative Azide–Alkene Cyclo-
addition: An Efficient Synthesis of Substituted 1,2,3-Triazoles
Donala Janreddy,a Veerababurao Kavala,a Chun-Wei Kuo,a Wen-Chang Chen,a
Chintakunta Ramesh,a Trimurtulu Kotipalli,a Ting-Shen Kuo,a Mei-Ling Chen,a
Chiu-Hui He,a and Ching-Fa Yaoa,*
a
Department of Chemistry, National Taiwan Normal University, 88, Sec. 4, Tingchow Road, Taipei, Taiwan 116, R.O.C.
E-mail: cheyaocf@ntnu.edu.tw
Received: April 22, 2013; Revised: July 11, 2013; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300344.
Abstract: A novel, copper(I)-promoted azide–alkene azides and electron-deficient olefins under an oxygen
aerobic oxidative cycloaddition protocol was devel- atmosphere.
oped for the regioselective synthesis of 1,4-disubsti-
tuted/1,4,5-trisubstituted 1,2,3-triazoles by using Keywords: aerobic oxidation; azide–alkene cycload-
dition; copper catalysis; 1,2,3-triazoles
Introduction
dition to form unstable regioisomeric triazolines,
which produce different products depending upon the
The 1,2,3-triazole motif occupies a special place in conditions employed (Scheme 2).[9]
heterocyclic chemistry, and is featured in a large
Johnston et al. reported that the Brønsted-acid pro-
number of bioactive molecules[1] as well as substances moted addition of azides on activated olefins (methyl
used in medicinal chemistry[2] and other research vinyl ketone) delivers the corresponding aziridines via
fields.[3] Among the various 1,2,3-triazoles, 1,4-disub- triazoline intermediates, whereas active ester deriva-
stituted/1,4,5-trisubstituted 1,2,3-triazole derivatives tives bearing a Lewis basic oxygen [such as methyl
have found broad applications in different areas such acryloylACTHNUGRTENUNG(benzyl)carbamates] readily participate in
as bioconjugations, polymers, pesticides, pharmaceuti- a tandem process to deliver oxazolidinedione com-
cals and surface science.[4] The most general method
for the synthesis of 1,2,3-triazoles is the Huisgen 1,3-
dipolar cycloaddition reactions between azide and
alkyne.[5] However, because of high activation ener-
gies and poor regioselectivity, the Huisgen 1,3-dipolar
cycloaddition has limited utilization in general synthe-
sis. Concurrently, the Cu(I)-catalyzed Huisgen 1,3-di-
polar cycloaddition of azide–alkyne (CuAAC, often
referred as click chemistry[6]) has been exposed and
became one of the most familiar and efficient ap-
proaches to the synthesis of substituted 1,2,3-triazoles,
but is generally restricted to terminal alkynes.
Alternatively, 1,2,3-triazole derivatives could also
be achieved from the 1,3-dipolar cycloaddition of
azides onto alkenes bearing the leaving group[7] [or
azides with push-pull alkene with a leaving group
(LG)] [Scheme 1, Eqs. (1) and (2)] and azides with a-
functionalized ketones/carbonyl compounds/1,3-dike-
tone/b-dicarbonyl compounds [Scheme 1, Eq. (3)].[8]
Moreover, the reaction of organic azides with elec-
tron-deficient olefins proceed via 1,3-dipolar cycload- from activated alkenes.
Scheme 1. Previous reports on substituted 1,2,3-triazoles
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knowledge, the synthesis of 1,4-disubstituted 1,2,3-tri-
azoles via oxidative cycloaddition of azides to elec-
tron-deficient terminal olefins has not been reported
in the literature. Recently, we became interested in
developing newer strategies for the construction of
variety of heterocyclic compounds via transition
metal catalysis.[13] In continuation to our interest on
this topic, we wanted to investigate the oxidative cy-
cloaddition of azides to electron-deficient olefins for
the synthesis of 1,4-disubstituted 1,2,3-triazole deriva-
tives.
Scheme 2. Previous reports on the reaction of electron-defi-
cient olefins with azides.
pounds.[10] In the mean time, Finney et al. reported
that the reaction of vinyl acetate with azides in the
presence of trimethyl or triethyl orthoformate at high Results and Discussion
temperature produced unstable triazoline intermedi-
ates, furthermore, they undergo elimination of an ace- To pursue our objective, we initially subjected methyl
tate group in the presence of acid or base to afford vinyl ketone to reaction with benzyl azide in the pres-
the corresponding triazoles.[11] In addition, recently, ence of copper iodide in THF solvent at room tem-
some groups reported on the regioselective synthesis perature for 12 h. Under these conditions, we ob-
of substituted 1,2,3-triazole derivatives from chal- tained a trace amount of the desired 1,4-disubstituted
cones and azides.[12] However, to the best of our 1,2,3-triazole (2a) (Table 1, entry 1). Next, we con-
Table 1. Optimization of the reaction conditions for 2a.
[a]
All the reactions were carried out under the following conditions, benzyl
azide (1.0 mmol), methyl vinyl ketone (3.0 mmol) and base (1.5 mmol) under
an air condenser.
Yields determined by H NMR (CH2Br2 as internal standard). Time and yield
[b]
1
given in parentheses refer to reactions conducted at room temperature.
Under a nitrogen atmosphere (N2).
Under an oxygen atmosphere (O2).
[c]
[d]
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Copper(I)-Catalyzed Aerobic Oxidative Azide–Alkene Cycloaddition
tion (entries 10 and 11), 1,4-dioxane turned out to be
the best solvent for this reaction and produced the
corresponding triazole derivative in good yield
(entry 12). Further improvement of the yield was ob-
served, when the reaction was conducted in the pres-
ence of 20 mol% of CuI at 808C in 1,4-dioxane sol-
vent (entry 17). Moreover, it is reported in the litera-
ture that the aromatization process proceeds smoothly
under copper catalysis in the presence of molecular
oxygen.[14] Hence, we performed the reaction in the
presence of molecular oxygen (entry 20). To our de-
light, the reaction furnished the desired 1,4-disubsti-
tuted 1,2,3-triazole product (2a) in excellent yield. In
all these reactions, we utilized 3.0 equiv. of methyl
Figure 1. ORTEP diagram of the single crystal X-ray diffrac-
tion structure of 2a.[18]
ducted the reaction by the addition of K2CO3 as base. vinyl ketone. We also conducted the reactions using
Under these conditions, the reaction produced a slight- lower amounts of methyl vinyl ketone (1.5 equiv.,
ly improved yield of the desired product (entry 2). To 2 equiv. and 2.5 equiv.). The reactions produced com-
screen the catalysts, we performed the reaction with partively low yields of desired product.This might be
other copper catalysts like CuBr and CuCl, respec- due to the polymerization of some amount of methyl
tively. However, there was no marked improvement vinyl ketone in the presence of copper iodide.[15] The
in the reaction was observed (entries 3 and 4). Fur- structure of the 1,4-disubstituted 1,2,3-triazole prod-
thermore, we screened the reaction with various bases uct (2a) was well characterized using all spectroscopic
like
[2.2.2]octane (DABCO), 1,8-diazabicyclo
7-ene (DBU), pyridine and N,N-diisopropylethyl- (Figure 1).
amine (DIPEA) (entries 5–9). Among the bases After the optimization of the reaction conditions,
triethylamine
(Et3N),
1,4-diazabicyclo- techniques and confirmed by 1H NMR, 13C NMR,
[5.4.0]undec- LR-MS, HR-MS and a single crystal X-ray analysis
G
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
tested in this reaction, DIPEA gave the best yield of different azides and electron-deficient olefins were
the product (entry 9). Next, we examined different used to evaluate the reaction scope. In this regard, we
solvents for this reaction, although polar solvents like first examined the reaction with a variety of electron-
DMSO and DMF are equally efficient for this reac- deficient olefins. As illustrated in Table 2, the reac-
Table 2. Substituted triazole formation from benzyl azide and various electron-deficient olefin-
s.[a,b]
[a]
All the reactions were conducted on a 2-mmol scale.
Isolated yields.
Reaction became messy.
[b]
[c]
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Table 3. Substrate scope of the reaction with various azides and electron-deficient terminal olefins.[a,b]
[a]
[b]
All the reactions were conducted on a 2-mmol scale.
Isolated yields.
tions of benzyl azide with a,b-unsaturated aldehyde
Once we had studied the efficacy of our method for
(acrolein) provided the corresponding triazole deriva- the different classes of electron-deficient alkenes and
tive in good yield (Table 2, 1a). It is important to note benzyl azide, we decided to establish the versatility of
that the yields of the desired product were high when our protocol using different azides. In this regard, we
the a,b-unsaturated ketones like methyl vinyl ketone, examined the reaction of various structurally diverse
ethyl vinyl ketone, and phenyl vinyl ketone were em- azides and electron-deficient alkenes. The results are
ployed as substrates in the reaction with benzyl azide summarized in Table 3. The reactions of benzyl azides
in the present reaction conditions (2a–4a). Further- equipped with electron-donating as well as electron-
more, when a,b-unsaturated amides were employed withdrawing groups reacted equally easily with
as substrates, the reaction provided the corresponding methyl vinyl ketone to produce their corresponding
triazole derivatives in moderate to good yields (5a triazole derivatives in moderate to good yields
and 6a). The reaction of benzyl azide with an a,b-un- (Table 3, 10a–14a). Interestingly, under the present re-
saturated thioester, that is, S-phenyl prop-2-ene- action conditions, the reaction of phenyl azide with
thioate produced the corresponding triazole product methyl vinyl ketone furnished the desired product in
in moderate yield (7a). On the other hand, the reac- good yield (15a). Importantly, the reactions of aliphat-
tions of benzyl azide with methyl/ethyl acrylate and ic azides with methyl vinyl ketone proceeded smooth-
acrylonitrile failed to form the desired 1,4-disubstitut- ly to afford the expected 1,4-disubstituted 1,2,3-tri-
ed 1,2,3-triazole products (8a and 9a).
ACHTUNGTRENNUNG
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Copper(I)-Catalyzed Aerobic Oxidative Azide–Alkene Cycloaddition
Table 4. Substrate scope of the reaction with various azides and internal olefins.[a,b]
[a]
All the reactions were conducted on a 2-mmol scale.
Isolated yields.
[b]
observed when ethyl vinyl ketone was used as sub- ternal olefins with various substituted azides under
strate (19a–22a). However, when phenyl vinyl ketone the optimal reaction conditions. To our delight, the
was used as substrate, the reaction took a longer time desired product was obtained in moderate yields in
compared with other electron-deficient alkenes (23a– most of the tested reactions. However, the reactions
27a). Notably, the functional groups like ester, cyano took a longer time (96 h) to produce the correspond-
and halogen survived under the present reaction con- ing triazole products than did the terminal olefins
ditions.
(Table 4, 31a–36a). The possible reason for the slow
Finally, to evaluate the scope of the present meth- reaction might be a steric effect of substituents at the
odology, we performed the reactions of substituted in- b-position of the carbonyl group. It is worthy to men-
Scheme 3. Plausible mechanism for the synthesis of 1,4-disubstituted/1,4,5-trisubstituted 1,2,3-triazoles.
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tion here that Baohua Chen and co-workers have ob- Experimental Section
tained N-2-aryl-substituted 1,2,3-triazole derivatives
via azide-chalcone oxidative cycloaddition and post- General Remarks
triazole arylation using similar conditions, however
Reagents and solvents were purchased from various com-
mercial sources and were used directly without any further
purification unless otherwise stated. Column chromatogra-
phy was performed with Merck silica gel 60 (230–400 mesh).
1H and 13C NMR spectra were recorded at 400 and
100 MHz, respectively. Chemical shifts are reported in parts
per million (d) using TMS and chloroform as an internal
standards and coupling constants are expressed in Hz. IR
spectra were recorded on an FT-IR spectrometer and are re-
ported in cmÀ1. Melting points were recorded using an elec-
tro thermal capillary melting point apparatus and are uncor-
rected.
they used sodium azide as component.[12a,c]
The plausible mechanism for the formation of 1,4-
disubstituted/1,4,5-trisubstituted 1,2,3-triazoles is out-
lined in Scheme 3.We assume that the reaction of an
electron-deficient alkene and azide could initially in-
volve stepwise 1,3-dipolar cycloaddition to produce
a triazoline intermediate (A). This triazoline inter-
mediate would be oxidzed in the presence of a copper
catalyst and molecular oxygen to generate intermedi-
ate (B). In the further course this intermediate B un-
dergoes deprotonation in the presence of base
(DIPEA) leading to generation of the desired prod-
uct. The failure in the production of 1,4-disubstituted
1,2,3-triazole derivatives (8a, 9a) from the reaction of
methyl acrylate, and acrylonitrile with benzyl azide
can be explained based on the mechanism as methyl
acrylate and acrylonitrile are weaker Michael accept-
ors than methyl/ethyl/phenyl vinyl ketones.[16] Thus,
the base-promoted stepwise 1,3-dipolar cycloaddition
may not taken place between weak Michael acceptors
and benzyl azide. Another reason may be that, even if
it forms the triazoline intermediate (A), the proton at
the a-carbon to ester and cyano functionalities in the
triazoline intermediate (A) is less acidic compared to
that with a keto functionality. Probably, the basicity
of DIEPA is not enough for the abstraction of the
proton at the a-carbon to ester and cyano functionali-
ties in the triazoline intermediate.
General Experimental Procedure for the Synthesis of
1,4-Disubstituted/1,4,5-Trisubstituted Triazoles
Copper(I) iodide (20 mol%) and N,N-diisopropylethylamine
(1.5 mmol) were added to a stirred solution of azide
(1 mmol) and electron-deficient olefin [acrolein or methyl
vinyl ketone (3.0 mmol), ethyl vinyl ketone (1.5 mmol),
phenyl
vinyl
ketone/acrylamide/N-phenylacrylamide/
prop-2-enethioate/chalcones
N-butylacrylamide/S-phenyl
(1.0 mmol)] in 1,4-dioxane solvent (5.0 mL) under an
oxygen atmosphere. The reaction mixture was then heated
to 808C and monitored by TLC. After completion of the re-
action, the reaction mixture was cooled to room tempera-
ture and the solvent was removed by vacuum evaporation.
The resulting crude product was purified by column chroma-
tography to afford the desired substituted 1,2,3-triazole.
Physical and Spectral Data
1-Benzyl-1H-1,2,3-triazole-4-carbaldehyde (1a):[17d] Yield:
75%; white dolid; mp 88–898C; FT-IR (KBr): n=1695 cmÀ1
;
1H NMR (400 MHz, CDCl3): d=10.11 (s, 1H), 7.99 (s, 1H),
Conclusions
7.41–7.39 (m, 3H), 7.31–7.28 (m, 2H), 5.58 (s, 2H);
In conclusion, we have successfully developed a novel 13C NMR (100 MHz, CDCl3): d=185.2, 148.2, 133.5, 129.6,
129.5, 128.5, 125.3, 54.8; LR-MS (ESI): m/z (relative intensi-
ty)=210 (M+ +Na, 48), 199 (12); HR-MS m/z=210.0647,
calcd. for C10H9N3ONa (M+ +Na): 210.0643.
method for the synthesis of a diverse array of regiose-
lective 1,4-disubstituted/1,4,5-trisubstituted 1,2,3-tria-
zoles through copper(I)-catalyzed aerobic oxidative
azide and alkene cycloaddition. This method involves
the 1,3-dipolar cycloaddition of alkene and azide fol-
lowed by aerobic oxidative aromatization in cascade
process. A wide range of terminal and internal elec-
tron-deficient alkenes and azides were investigated in
this reaction. Moderate to excellent yields of 1,2,3-tri-
1-(1-Benzyl-1H-1,2,3-triazol-4-yl)ethan-1-one
Yield: 87%; white solid; mp 91–928C; FT-IR (KBr): n=
1685 cmÀ1 1H NMR (400 MHz, CDCl3): d=7.94 (s, 1H),
(2a):[7c,17e]
;
7.39–7.37 (m, 3H), 7.29–7.27 (m, 2H), 5.55 (s, 2H), 2.66 (s,
3H); 13C NMR (100 MHz, CDCl3): d=193.0, 148.6, 133.8,
129.5, 129.3, 128.5, 125.4, 54.7, 27.3; LR-MS (EI): m/z (rela-
tive intensity)=201.1 (M+, 15), 172.1 (100), 130.1 (26); HR-
azole derivatives obtained. We believe this procedure MS: m/z=201.0908, calcd. for C11H11O1N3 (M+): 201.0902.
1-(1-Benzyl-1H-1,2,3-triazol-4-yl)propan-1-one
(3a):[17c]
offers an easy and convenient alternative to the exist-
ing methodologies for the synthesis of 1,2,3-triazole
derivatives.
Yield: 82%; white solid; mp 116–1178C; FT-IR (KBr): n=
1688 cmÀ1 1H NMR (400 MHz, CDCl3): d=7.96 (s, 1H),
;
7.43–7.40 (m, 3H), 7.35–7.30 (m, 2H), 5.57 (s, 2H), 3.15 (q,
J=7.45 Hz, 2H), 1.22 (t, J=7.34 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=196.0, 148.2, 133.9, 129.5, 129.3,
128.5, 125.3, 54.6, 33.0, 7.94. LR-MS (EI): m/z (relative in-
tensity)=215.2 (M+, 35), 186.1 (98); HR-MS: m/z=
215.1057. calcd. for C12H13O1N3 (M+): 215.1059.
4-Benzoyl-1-benzyl-1H-1,2,3-triazole (4a): Yield: 85%;
white solid; mp 115–1168C; FT-IR (KBr): n=1635 cmÀ1
;
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Copper(I)-Catalyzed Aerobic Oxidative Azide–Alkene Cycloaddition
1H NMR (400 MHz, CDCl3): d=8.42–8.40 (m, 2H), 8.16 (s,
1H), 7.60–7.58 (m, 1H), 7.53–7.41 (m, 2H), 7.41–7.39 (m,
3H), 7.34–7.32 (m, 2H), 5.60 (s, 2H); 13C NMR (100 MHz,
CDCl3): d=185.8, 148.6, 136.7, 133.9, 133.4, 130.7, 129.5,
129.4, 129.3, 128.5, 128.4, 54.6; LR-MS (EI): m/z (relative in-
tensity)=263 (M+, 81), 234 (100), 206.(42), 116 (42); HR-
MS: m/z=263.1056, calcd. for C16H13O1N3 (M+): 263.1059.
1-Benzyl-1H-1,2,3-triazole-4-carboxamide (5a): Yield:
65%; white solid; mp 243–2448C; FT-IR (KBr): n=3394,
1-{1-[(4-Fluorophenyl)methyl]-1H-1,2,3-triazol-4-yl}ethan-
1-one (13a): Yield: 70%; brown gummy solid; FT-IR (KBr):
1
n=1685 cmÀ1; H NMR (400 MHz, CDCl3): d=7.95 (s, 1H),
7.30–7.27 (m, 2H), 7.09–7.05 (m, 2H), 5.53 (s, 2H), 2.66 (s,
3H); 13C NMR (100 MHz, CDCl3): d=192.7, 163 (d, J=
247 Hz), 148.4, 130.2 (d, J=8 Hz), 129.5 (d, J=3 Hz), 125.1,
116.3
(d,
J=21 Hz), 53.7, 27.0;
LR-MS
(EI):
m/z (relative intensity)=219 (M+, 5), 190.1 (48), 109.1
(100); HR-MS: m/z=219.0803, calcd. for C11H10O1N3F
(M+): 219.0808.
1701 cmÀ1 1H NMR (400 MHz, CDCl3): d=7.97 (s, 1H),
;
7.40–7.38 (m, 3H), 7.30–7.28 (m, 2H), 7.02 (s, 1H), 5.55 (s,
3H); 13C NMR (100 MHz, CDCl3 and CD3OD): d=162.8,
142.6, 133.8, 129.1, 128.9, 128.0, 126.1, 54.3; LR-MS (ESI):
m/z (relative intensity)=203 (M+ +H, 31), 225 (M+ +Na,
40), 132 (20); HR-MS: m/z=202.0850, calcd. for C10H10O1N4
(M+): 202.0855.
1-{1-[(4-Chlorophenyl)methyl]-1H-1,2,3-triazol-4-yl}ethan-
1-one (14a): Yield: 74%; white solid; mp 125–1268C; FT-IR
1
(KBr): n=1684 cmÀ1; H NMR (400 MHz, CDCl3): d=7.95
(s, 1H), 7.37–7.35 (m, 2H), 7.26–7.22 (m, 2H), 5.53 (s, 2H),
2.67 (s, 3H); 13C NMR (100 MHz, CDCl3): d=192.9, 148.7,
135.5, 132.3, 129.8, 129.7, 125.3, 53.9, 27.3; LR-MS (EI): m/z
(relative intensity)=235 (M+, 5), 125 (100); HR-MS: m/z=
235.0515, calcd. for C11H10O1N3Cl1 (M+): 235.0512.
1-Benzyl-N-phenyl-1H-1,2,3-triazole-4-carboxamide
(6a):[17a] Yield: 75%; white solid; mp 189–1908C; FT-IR
1
(KBr): n=3343, 1662 cmÀ1; H NMR (400 MHz, CDCl3): d=
1-(1-Phenyl-1H-1,2,3-triazol-4-yl)ethan-1-one
Yield: 80%; white solid; mp 108–1098C; FT-IR (KBr): n=
1691 cmÀ1 1H NMR (400 MHz, CDCl3): d=8.48 (s, 1H),
(15a):[17i]
8.93 (brs, 1H), 8.05 (s, 1H), 7.68–7.66 (m, 2H), 7.42–7.30
(m, 7H), 7.16–7.12 (m, 1H), 5.58 (s, 2H); 13C NMR
(100 MHz, CDCl3): d=157.9, 143.9, 137.6, 133.8, 129.5,
129.4, 129.3, 128.5, 125.9, 124.7, 120.0, 54.8; LR-MS (ESI):
m/z (relative intensity)=279 (M+ +H, 40), 301 (M+ +Na,
20); HR-MS: m/z=278.1154, calcd. for C16H14O1N4 (M+):
278.1168.
;
7.76–7.74 (m, 2H), 7.58–7.54 (m, 2H), 7.51–7.47 (m, 1H),
2.75 (s, 3H); 13C NMR (100 MHz, CDCl3): d=193.0, 148.7,
136.6, 130.1, 129.7, 123.5, 121.0, 27.4; LR-MS (ESI): m/z
(relative intensity)=188 (M+ +H, 100), 174 (50), 164 (85);
HR-MS: m/z=187.0741, calcd. for C10H9O1N3 (M+):
187.0746.
(1-Benzyl-1H-1,2,3-triazol-4-yl)(phenylsulfanyl)methan-
one (7a): Yield: 60%; white solid; mp 143–1448C; FT-IR
1-[1-(2-Phenylethyl)-1H-1,2,3-triazol-4-yl]ethan-1-one
(16a): Yield: 75%; white solid; mp 114–1158C; FT-IR
(KBr): n=1672cmÀ1 1H NMR (400 MHz, CDCl3): d=7.95
;
1
(s, 1H), 7.52–7.48 (m, 2H), 7.44–7.43 (m, 3H), 7.40–7.38 (m,
3H), 7.30–7.28 (m, 2H), 5.58 (s, 2H); 13C NMR (100 MHz,
CDCl3): d=183.4, 146.5, 135.2, 133.7, 129.8, 129.5, 129.4,
129.4, 128.4, 126.7, 124.4, 54.8; LR-MS (ESI); m/z (relative
intensity)=296 (M+ +H, 100), 268 (5); HR-MS: m/z=
296.0865, calcd. for C16H14S1O1N3 (M+ +H): 296.0858.
(KBr): n=1683 cmÀ1; H NMR (400 MHz, CDCl3): d=7.76
(s, 1H), 7.31–7.24 (m, 3H), 7.24–7.07 (m, 2H), 4.63 (t, J=
7.18 Hz, 2H), 3.23 (t, J=7.18 Hz, 2H), 2.66 (s, 3H);
13C NMR (100 MHz CDCl3): d=193.0, 148.0, 136.5, 129.1,
128.7, 127.5, 125.7, 52.1, 36.6, 27.3; LR-MS (EI): m/z (rela-
tive intensity)=215.2 (M+, 4), 104 (100); HR-MS: m/z=
215.1059, calcd. for C12H14O1N3 (M+): 215.1059.
1-{1-[(4-Methoxyphenyl)methyl]-1H-1,2,3-triazol-4-yl}-
ethan-1-one (10a): Yield: 60%; white solid; mp 111–1128C;
4-(4-Acetyl-1H-1,2,3-triazol-1-yl)butanenitrile
Yield: 75%; white solid; mp 70–718C; FT-IR (KBr): n=
2250, 1679 cmÀ1 1H NMR (400 MHz, CDCl3): d=8.11 (s,
(17a):
FT-IR (KBr): n=1687 cmÀ1 1H NMR (400 MHz, CDCl3):
;
d=7.90 (s, 1H), 7.26–7.23 (m, 2H), 6.91–6.89 (m, 2H), 5.48
(s, 2H), 3.80 (s, 3H), 2.66 (s, 3H); 13C NMR (100 MHz
CDCl3): d=193.1, 160.4, 148.5, 130.1, 125.7, 125.2, 114.9,
55.5, 54.2, 27.3; LR-MS (EI): m/z (relative intensity)=231.1
(M+, 25), 202.1 (88), 121.1 (100); HR-MS: m/z=231.1007,
calcd. for C12H13O2N3 (M+): 231.1008.
;
1H), 4.57 (t, J=6.56 Hz, 2H), 2.69 (s, 3H), 2.47–2.43 ( m,
2H), 2.38–2.33 (m, 2H); 13C NMR (100 MHz, CDCl3): d=
192.8, 148.5, 125.9, 118.0, 48.8, 27.3, 26.0, 14.8; LR-MS (EI):
m/z (relative intensity)=179 (M+ +H,5), 135.1 (100); HR-
MS (FAB): m/z=179.0934, calcd. for C8H11O1N4 (M+):
179.0933.
1-{1-[(4-Methylphenyl)methyl]-1H-1,2,3-triazol-4-yl}-
ethan-1-one (11a): Yield: 72%; white solid; mp 102–1038C;
1-(1-Hexyl-1H-1,2,3-triazol-4-yl)ethan-1-one (18a): Yield:
FT-IR (KBr): n=1685 cmÀ1
;
1H NMR (400 MHz, CDCl3):
65%; white solid; mp 63–648C; FT-IR (KBr): n=1685 cmÀ1
;
d=7.91 (s, 1H), 7.18–7.13 (m, 4H), 5.50 (s, 2H), 2.66 (s,
3H), 2.35 (s, 3H); 13C NMR (100 MHz, CDCl3): d=193.0,
148.5, 139.4, 130.7, 130.2, 128.6, 125.3, 54.5, 27.3, 21.3; LR-
MS (EI): m/z (relative intensity)=215 (M+, 10), 105 (100),
172 (46); HR-MS: m/z=215.1057, calcd. for C12H13O1N3
(M+): 215.1059.
1H NMR (400 MHz, CDCl3): d=8.03 (s, 1H), 4.39 (t, J=
7.22 Hz, 2H), 2.68 (s, 3H), 1.93–1.89 ( m, 2H), 1.33–1.24 (m,
6H), 0.85 (t, J=6.73 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d=193.2, 148.3, 125.2, 50.8, 31.2, 30.2, 27.3, 26.2, 22.5, 14.0;
LR-MS (EI): m/z (relative intensity)=195.2 (M+, 13), 152.2
(76), 124.2 (100); HR-MS: m/z=195.1368, calcd. for
C10H17O1N3 (M+): 195.1372.
1-{1-[(4-tert-Butylphenyl)methyl]-1H-1,2,3-triazol-4-yl}-
ethan-1-one (12a): Yield: 65%; white solid; mp 117–1188C;
1-{1-[(4-Methoxyphenyl)methyl]-1H-1,2,3-triazol-4-yl}pro-
pan-1-one (19a): Yield: 72%; brown solid; mp 113–1148C;
FT-IR (KBr): n=1688 cmÀ1 1H NMR (400 MHz, CDCl3):
;
d=7.92 (s, 1H), 7.41–7.39 (m, 2H), 7.24–7.22 (m,2H), 5.52
(s, 2H), 2.67 (s, 3H), 1.31 (s, 9H); 13C NMR (100 MHz,
CDCl3): d=193.1, 152.6, 148.5, 130.7, 128.4, 126.5, 125.4,
54.4, 34.9, 31.4, 27.3; LR-MS (EI): m/z (relative intensity)=
257.2 (M+, 10), 172.1 (100), 147.2 (98); HR-MS: m/z=
257.1526, calcd. for C15H19O1N3 (M+): 257.1528.
FT-IR (KBr): n=1692 cmÀ1 1H NMR (400 MHz, CDCl3):
;
d=7.90 (s, 1H), 7.25–7.23 (m, 2H), 6.91–6.89 (m, 2H), 5.48
(s, 2H), 3.80 (s, 3H), 3.12 (q, J=7.38 Hz, 2H) 1.20 (t, J=
7.34 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=196.0, 160.4,
148.2, 130.1, 125.8, 125.1, 114.9, 55.5, 54.2, 33.0, 7.9; LR-MS
(EI): m/z (relative intensity)=245.2 (M+, 16), 202.1 (45),
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Donala Janreddy et al.
FULL PAPERS
1
121.2 (100); HR-MS: m/z=245.1166, calcd. for C13H15O2N3
(M+): 245.1164.
2248, 1651 cmÀ1; H NMR (400 MHz, CDCl3): d=8.44–8.42
(m, 2H), 8.31 (s, 1H), 7.66–7.62 (m, 1H), 7.56–7.52 (m, 2H)
4.63 (t, J=6.56 Hz, 2H), 2.52–2.49 (m, 2H), 2.44–2.39 ( m,
2H); 13C NMR (100 MHz, CDCl3): d=185.6, 148.6, 136.5,
133.6, 130.8, 128.9, 128.6, 118.0, 48.8, 26.1, 14.9; LR-MS
(FAB): m/z (relative intensity)=241 (M+ +H, 35), 105
(100); HR-MS (FAB): calcd. for C13H13O1N4 (M+ +H):
241.1089.
1-[1-(2-Phenylethyl)-1H-1,2,3-triazol-4-yl]propan-1-one
(20a): Yield: 65%; brown gummy solid; FT-IR (KBr): n=
1690 cmÀ1 1H NMR (400 MHz, CDCl3): d =7.77 (s, 1H),
;
7.29–7.25 (m, 3H), 7.09–7.07 (m, 2H), 4.63 (t, J=7.22 Hz,
2H), 3.22 (t, J=7.18 Hz, 2H), 3.13 (q, J=7.32 Hz, 2H), 1.20
(t, J=7.32 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=196.0,
147.7, 136.6, 129.1, 128.7, 127.5, 125.7, 52.1, 36.7, 33.0, 7.9;
LR-MS (EI): m/z (relative intensity)=229 (M+, 5), 105
(100), 138 (35); HR-MS: m/z=229.1211, calcd. for
C13H15O1N3 (M+): 229.1215.
4-Benzoyl-1-hexyl-1H-1,2,3-triazole (27a): Yield: 78%;
yellow solid; mp 48–498C; FT-IR (KBr): n=1643 cmÀ1
;
1H NMR (400 MHz, CDCl3): d=8.44–8.42 (m, 2H), 8.24 (s,
1H), 7.63–7.59 (m, 1H), 7.53–7.49 ( m, 2H), 4.44 (t, J=
7.22 Hz, 2H), 2.00–1.92 (m, 2H), 1.37–1.30 (m, 6H), 0.88 (t,
J=7.62 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=185.9,
148.3, 136.8, 133.4, 130.8, 128.5, 128.3, 50.8, 31.2, 30.3, 26.2,
22.5, 14.1; LR-MS (ESI): m/z (relative intensity)=258
(M+ +H, 3), 280 (M+ +Na, 5); HR-MS: m/z=258.1600,
calcd. for C15H20O1N3 (M+ +H): 258.1606.
1-(1-Hexyl-1H-1,2,3-triazol-4-yl)propan-1-one
Yield: 60%; yellow solid; mp 47–488C; FT-IR (KBr): n=
1679 cmÀ1 1H NMR (400 MHz, CDCl3): d=8.03 (s, 1H),
(21a):
;
4.38 (t, J=7.24 Hz, 2H), 3.14 (q, J=7.28 Hz, 2H), 1.95–1.87
( m, 2H), 1.33–1.23 (m, 6H), 1.21 (t, J=7.38 Hz, 3H), 0.87
(t, J=7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=196.2,
147.9, 125.2, 50.8, 32.9, 31.2, 30.3, 26.2, 22.5, 14.1, 7.9; LR-
MS (ESI): m/z (relative intensity)=232 (M+ +Na, 57), 273
(100), 347 (40); HR-MS: m/z=232.1425, calcd. for
C11H19O1N3Na (M+ +Na): 232.1426.
1-Benzyl-N-butyl-1H-1,2,3-triazole-4-carboxamide (28a):
Yield: 65%; white solid; mp 164–1658C; FT-IR (KBr): n=
3318, 1647 cmÀ1 1H NMR (400 MHz, CDCl3): d=7.94 (s,
;
1H), 7.38–7.36 (m, 3H), 7.28–7.26 (m, 2H), 7.14 (brs, 1H),
5.53 (s, 2H), 3.42 (q, J=6.7 Hz, 2H), 1.61–1.54 (m, 2H)
1.44–1.35 (m, 2H), 0.93 (t, J=7.32 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=160.1, 144.0, 134.0, 129.4, 129.3,
128.4, 125.3, 54.7, 39.0, 31.8, 20.2, 13.9; LR-MS (ESI): m/z
(relative intensity=259 (M+ +H, 100), 233 (15); HR-MS:
m/z=258.1468, calcd. for C14H18O1N4 (M+): 258.1481.
1-(1-Phenyl-1H-1,2,3-triazol-4-yl)propan-1-one
Yield: 72%; white solid; mp 142–1438C; FT-IR (KBr): n=
1679 cmÀ1 1H NMR (400 MHz, CDCl3): d=8.48 (s, 1H),
(22a):
;
7.76–7.74 (m, 2H), 7.58–7.54 (m, 2H), 7.51–7.47 (m, 1H),
3.22 (q, J=7.34 Hz, 2H), 1.26 (t, J=7.32 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=196.0, 148.4, 136.6, 130.1, 129.7,
123.5, 121.0, 33.2, 7.9; LR-MS (ESI): m/z (relative intensi-
ty)=202 (M+ +H, 40), 132 (50); HR-MS: m/z=201.0893,
calcd. for C11H11O1N3 (M+): 201.0902.
(1-Hexyl-1H-1,2,3-triazol-4-yl)(phenylsulfanyl)methanone
(29a): Yield: 55%; white solid; mp 63–648C; FT-IR (KBr):
n=1672 cmÀ1; H NMR (400 MHz, CDCl3): d=8.03 (s, 1H),
1
4-Benzoyl-1-[(4-methoxyphenyl)methyl]-1H-1,2,3-triazole
7.54–7.51 (m, 2H), 7.41–7.37 (m, 1H), 7.46–7.43 ( m, 2H),
4.41 (t, J=7.22 Hz, 2H), 1.96–1.89 (m, 2H), 1.34–1.29 (m,
6H), 0.88 (t, J=6.84 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d=183.6, 146.1, 135.2, 129.8, 129.4, 126.8, 124.3, 51.0, 31.2,
30.3, 26.2, 22.5, 14.1; LR-MS (ESI): m/z (relative intensi-
ty)=290 (M+ +H, 100); HR-MS: m/z=290.1335, calcd. for
C15H20O1S1N3 (M+ +H): 290.1327.
(23a):[17c] Yield: 70%; white solid; mp 118–1198C; FT-IR
1
(KBr): n=1640 cmÀ1; H NMR (400 MHz, CDCl3): d=8.41–
8.39 (m, 2H), 8.12 (s, 1H), 7.61–7.58 (m, 1H), 7.52–7.48 (m,
2H), 7.29–7.26 (m, 2H), 6.93–6.90 (m, 2H) 5.53 (s, 2H), 3.81
(s, 3H); 13C NMR (100 MHz, CDCl3): d=185.9, 160.4, 130.7,
148.4, 136.7, 133.4, 130.7, 130.2, 128.5, 128.2, 125.8, 114.9,
55.5, 54.2; LR-MS (EI): m/z (relative intensity)=293 (M+,
6), 121 (100); HR-MS: m/z=293.1156, calcd. for C17H15O2N3
(M+): 293.1164.
1-(1-Benzyl-5-methyl-1H-1,2,3-triazol-4-yl)ethan-1-one
(30a):[17b] Yield: 65%; white solid; mp 148–1498C; FT-IR
1
(KBr): n=1680 cmÀ1; H NMR (400 MHz, CDCl3): d=7.35–
4-Benzoyl-1-[(4-methylphenyl)methyl]-1H-1,2,3-triazole
(24a): Yield: 70%; white solid; mp 113–1148C; FT-IR
7.26 (m, 3H), 7.17–7.16 (m, 2H), 5.51 (s, 2H), 2.69 (s, 3H),
2.46 (s, 3H); 13C NMR (100 MHz, CDCl3): d=194.6, 144.2,
137.0, 134.1, 129.3, 128.6, 127.4, 51.9, 27.9, 9.3; LR-MS (EI):
m/z (relative intensity)=215 (M+, 37), 186 (100); HR-MS:
m/z=215.1054, calcd. for C12H13O1N3 (M+): 215.1059.
1
(KBr): n=1639 cmÀ1; H NMR (400 MHz, CDCl3): d=8.41–
8.40 (m, 2H), 8.12 (s, 1H), 7.60–7.58 (m, 1H), 7.52–7.49 (m,
2H), 7.26–7.24 (m, 1H), 7.22–7.20 (m, 3H), 5.56 (s, 2H),
2.36 (s, 3H); 13C NMR (100 MHz, CDCl3): d=185.9, 148.5,
139.4, 136.7, 133.4, 130.8, 130.8, 130.2, 128.6, 128.5, 128.3,
54.5, 21.3; LR-MS (EI): m/z (relative intensity)=277 (M+,
62), 248 (45), 105 (100); HR-MS: m/z=277.1218, calcd. for
C17H15ON3 (M+): 277.1215.
1-(1-Benzyl-5-phenyl-1H-1,2,3-triazol-4-yl)ethan-1-one
(31a):[17g] Yield: 70%; yellow liquid; FT-IR (KBr): n=
1689 cmÀ1 1H NMR (400 MHz, CDCl3): d=7.49–7.39 (m,
;
3H), 7.26–7.23 (m, 3H), 7.19–7.17 (m, 2H), 7.01–6.99 (m,
2H), 5.40 (s, 2H), 2.66 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=192.9, 144.0, 139.7, 134.8, 130.3, 129.8, 129.0,
128.8, 128.6, 127.7, 126.2, 52.1, 28.2; LR-MS (ESI): m/z (rel-
ative intensity)=300 (M+ +Na, 100), 273 (15), 232 (20);
HR-MS: m/z=300.1115, calcd. for C17H15O1N3Na (M+ +
Na): 300.1113.
Ethyl 2-(4-benzoyl-1H-1,2,3-triazol-1-yl)acetate (25a):[17h]
Yield: 65%; yellow solid; mp 125–1268C; FT-IR (KBr): n=
1
1754, 1647 cmÀ1; H NMR (400 MHz, CDCl3): d=8.42–8.40
(m, 3H), 7.63–7.59 (m, 1H), 7.54–7.50 (m, 2H), 5.25 (s, 2H),
4.29 (q, J=6.14 Hz, 2H), 1.31 (t, J=7.18 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=185.6, 165.8, 148.6, 136.6, 133.5,
130.7, 130.0, 128.6, 62.9, 51.2, 14.2; LR-MS (ESI): m/z (rela-
tive intensity)=282 (M+ +Na, 45); HR-MS; m/z=282.0849,
calcd. for C13H13O1N3Na (M+ +Na): 282.0855.
4-Benzoyl-1-benzyl-5-phenyl-1H-1,2,3-triazole
Yield: 68%; white solid; mp 114–1158C; FT-IR (KBr): n=
1655 cmÀ1 1H NMR (400 MHz, CDCl3): d=8.29–8.27 (m,
(32a):[17f]
;
2H), 7.59–7.55 (m, 1H), 7.49–7.42 (m, 5H), 7.30–7.25 (m,
5H), 7.07–7.05 (m, 2H), 5.47 (s, 2H); 13C NMR (100 MHz,
CDCl3): d=186.5, 144.0, 142.0, 137.3, 134.8, 133.1, 130.8,
4-(4-Benzoyl-1H-1,2,3-triazol-1-yl)butanenitrile
(26a):
Yield: 70%; white solid; mp 85–868C; FT-IR (KBr): n=
8
asc.wiley-vch.de
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Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
These are not the final page numbers!

Copper(I)-Catalyzed Aerobic Oxidative Azide–Alkene Cycloaddition
130.2, 129.9, 129.0, 128.8, 128.6, 128.4, 127.8, 126.5, 52.2;
Merkx, C. Versluis, A. Eek, G. E. Mulder, D. T. S. Rijk-
ers, O. C. Boerman, R. M. J. Liskamp, J. Med. Chem.
2010, 53, 3944; c) R. P. Tripathi, A. K. Yadav, A. Ajay,
S. S. Bisht, V. Chaturvedi, S. K. Sinha, Eur. J. Med.
Chem. 2010, 45, 142; d) M. Meldal, C. W. Tornoe,
Chem. Rev. 2008, 108, 2952; e) M. I. Garcia-Moreno, D.
Rodriguez-Lucena, C. O. Mellet, J. M. G. Fernandez, J.
Org. Chem. 2004, 69, 3578.
LR-MS (ESI): m/z (relative intensity)=362 (M+ +Na, 45),
340
C22H17Cl1O1N3Na (M+ +Na): 362.1269.
4-Benzoyl-1-[(4-tert-butylphenyl)methyl]-5-phenyl-1H-
1,2,3-triazole (33a): Yield: 62%; yellow liquid; FT-IR (KBr):
n=1656 cmÀ1 1H NMR (400 MHz, CDCl3): d=8.29–8.27
(25);
HR-MS:
m/z=362.1271,
calcd.
for
;
(m, 2H), 7.58–7.54 (m, 1H), 7.50–7.46 (m, 5H), 7.46–7.43
(m, 4H), 7.03–7.01 (m, 2H), 5.43 (s, 2H), 1.29 (s, 9H);
13C NMR (100 MHz, CDCl3): d=186.5, 151.7, 143.9, 141.9,
137.3, 133.1, 131.8, 130.8, 130.1, 130.0, 128.8, 128.3, 127.7,
126.6, 125.9, 51.9, 35.0, 31.4; LR-MS (ESI): m/z (relative in-
tensity)=396 (M+ +H, 5), 370 (20); HR-MS: m/z=
396.2071, calcd. for C26H26O1N3 (M+ +H): 396.2076.
[2] a) H. Chen, J. L. Taylor, S. R. Abrams, Bioorg. Med.
Chem. Lett. 2007, 17, 1979; b) A. Sugawara, T. Sunazu-
ka, T. Hirose, K. Nagai, Y. Yamaguchi, H. Hanaki,
K. B. Sharpless, S. Omura, Bioorg. Med. Chem. Lett.
2007, 17, 6340; c) V. D. Bock, D. Speijer, H. Hiemstra,
J. H. Van Maarseveen, Org. Biomol. Chem. 2007, 5,
971; d) J. Wang, G. Sui, V. P. Mocharla, R. J. Lin, M. E.
Phelps, H. C. Kolb, H.-R. Tseng, Angew. Chem. 2006,
118, 5402; Angew. Chem. Int. Ed. 2006, 45, 5276; e) R.
Manetsch, A. Krasiski, Z. Radi, J. Raushel, P. Taylor,
K. B. Sharpless, H. C. Kolb, J. Am. Chem. Soc. 2004,
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[3] For reviews, see: Chem. Soc. Rev. 2010, 39, issue 4;
a) S. Wacharasindhu, S. Bardhan, Z.-K. Wan, K. Tabei,
T. S. Mansour, J. Am. Chem. Soc. 2009, 131, 4174;
b) J. E. Moses, A. D. Moorhouse, Chem. Soc. Rev. 2007,
36, 1249; c) P. Wu, V. V. Fokin, Aldrichimica Acta 2007,
40, 7; d) V. D. Bock, H. Hiemstra, J. H. Van Maar-
seveen, Eur. J. Org. Chem. 2006, 51; e) N. J. Agard,
J. A. Prescher, C. R. Bertozzi, J. Am. Chem. Soc. 2004,
126, 15046; f) H. C. Kolb, P. Wu, A. K. Feldman, A. K.
Nugent, C. J. Hawker, A. Scheel, B. Voit, J. Pyun,
J. M. J. Frechet, K. B. Sharpless, V. V. Fokin, Angew.
Chem. 2004, 116, 4018; Angew. Chem. Int. Ed. 2004, 43,
3928; g) H. C. Kolb, K. B. Sharpless, Drug Discovery
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V. V. Fokin, K. B. Sharpless, Angew. Chem. 2002, 114,
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hadolnik, A. D. DeBellis, M. G. Wood, J. Lau, J. Phys.
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tuted 1,2,3-triazoles, see: a) C. Spiteri, J. E. Moses,
Angew. Chem. 2010, 122, 33; Angew. Chem. Int. Ed.
2010, 49, 31; b) Y. Zhou, T. Lecourt, L. Micouin,
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Hiemstra, J. H. Van Maarseveen, Org. Lett. 2006, 8,
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Med. Chem. 1994, 37, 4185.
4-Benzoyl-1-benzyl-5-(4-chlorophenyl)-1H-1,2,3-triazole
(34a):[12d] Yield: 60%; yellow solid; mp 130–1318C; FT-IR
1
(KBr): n=1655 cmÀ1; H NMR (400 MHz, CDCl3): d=8.30–
8.28 (m, 2H), 7.52–7.45 (m, 5H), 7.29–7.24 (m, 5H), 7.07–
7.04 ( m, 2H), 5.46 (s, 2H); 13C NMR (100 MHz, CDCl3):
d=185.0, 143.7, 142.2, 139.6, 135.6, 134.7, 132.3, 130.3, 129.9,
129.0, 128.9, 128.7, 127.8, 126.4, 52.2; LR-MS (ESI): m/z
(relative intensity)=396 (M+ +Na, 45), 376 (5), 374 (7);
HR-MS: m/z=396.0872, calcd. for C22H16O1N3ClNa (M+ +
Na): 396.0880.
1-Benzyl-5-(4-methoxyphenyl)-4-[(4-methylphenyl)car-
bonyl]-1H-1,2,3-triazole (35a): Yield: 50%; yellow liquid;
FT-IR (KBr): n=1651 cmÀ1 1H NMR (400 MHz, CDCl3):
;
d=8.21–8.19 (m, 2H), 7.30–7.28 (m, 4H), 7.28–7.26 (m,
1H), 7.21–7.19 (m, 2H), 7.10–7.08 (m, 2H), 6.96–6.94 (m,
2H), 5.46 (s, 2H), 3.85 (s, 3H), 2.41 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=186.3, 161.0, 144.0, 143.9, 141.7,
135.1, 134.9, 131.5, 131.0, 129.1, 129.0, 128.5, 127.7, 118.3,
114.3, 55.5, 52.0, 21.9; LR-MS (ESI): m/z (relative intensi-
ty)=406 (M+ +Na, 62), 288 (8), 201 (10); HR-MS: m/z=
406.1530, calcd. for C24H21O2N3Na (M+ +Na): 406.1531.
[1-(4-Methoxybenzyl)-5-phenyl-1H-1,2,3-triazol-4-yl]-
ACHTUNGTRENNUNG
;
CDCl3): d=8.28–8.26 (m, 2H), 7.58–7.54 (m, 1H), 7.50–7.43
(m, 5H), 7.28–7.26 (m, 2H), 7.01–6.98 (m, 2H), 6.81–6.78
(m, 2H), 5.40 (s, 2H), 3.77 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=186.5, 159.8, 144.0, 141.7, 137.3, 133.1, 130.8,
130.1, 130.0, 129.4, 128.8, 128.3, 126.8, 126.7, 114.3, 55.4,
51.7; LR-MS (FAB): m/z (relative intensity)=370 (M+ +H,
100), 344 (10), 304 (8); HR-MS (FAB): m/z=370.1552,
calcd. for C23H20O2N3 (M+ +H): 370.1556.
Acknowledgements
Financial support for this work by the National Science
Council of the Republic of China (NSC 99-2119M-003-003-
MY2), National Taiwan Normal University (99T3030-2, 99-
D, 100-D-06) and Instrumentation Centre at National Taiwan
Normal University is gratefully acknowledged.
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Copper(I)-Catalyzed Aerobic Oxidative Azide–Alkene
Cyclo-addition: An Efficient Synthesis of Substituted 1,2,3-
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