Regioselective ortho-Acylation of N-Aryl-1,2,3-triazoles with Alcohols in Water

Article abstract of DOI:10.1002/ejoc.201600479

A palladium-catalyzed regioselective ortho-acylation of N-aryl-1,2,3-triazoles has been achieved under aqueous conditions without the assistance of surfactants or additives. The reaction takes place by using benzylic, heterocyclic, and aliphatic alcohols as the acylating reagents and tert-butyl hydroperoxide (TBHP) as the oxidant and provides an alternative route for the synthesis of triazole-substituted aryl, heteroaryl, and aliphatic ketones in moderate to excellent yields.

Full text of DOI:10.1002/ejoc.201600479

DOI: 10.1002/ejoc.201600479
Full Paper
C–H Acylation
Regioselective ortho-Acylation of N-Aryl-1,2,3-triazoles with
Alcohols in Water
Chanchal Premi,[a] Shyam Sunder Patel,[a] and Nidhi Jain*[a]
Abstract: A palladium-catalyzed regioselective ortho-acylation phatic alcohols as the acylating reagents and tert-butyl hydro-
of N-aryl-1,2,3-triazoles has been achieved under aqueous con- peroxide (TBHP) as the oxidant and provides an alternative
ditions without the assistance of surfactants or additives. The route for the synthesis of triazole-substituted aryl, heteroaryl,
reaction takes place by using benzylic, heterocyclic, and ali- and aliphatic ketones in moderate to excellent yields.
Introduction
tempted the synthesis of triazole-substituted aryl ketones in
water by employing a Pd-catalyzed C–H functionalization strat-
egy (Scheme 1). We chose to examine 1,2,3-triazoles because
of their synthetic utility as building blocks in medicinal and
materials chemistry.[20,21] To the best of our knowledge, there
are no prior reports of the acylation of N-aryltriazoles in water.
Palladium-catalyzed and directing-group-assisted C–H function-
alizations have led to new synthetic organic chemistry strate-
gies for the direct conversion of carbon–hydrogen bonds into
carbon–carbon and carbon–heteroatom bonds.[1] Among the
various ligand-assisted C–H activation methods, ortho-function-
alization is the most promising approach because of its capacity
for excellent regioselectivity and reactivity.[2] Recently, a fair
amount of literature regarding Pd-catalyzed acylations of aro-
matic C–H bonds with the assistance of directing groups such
as those of 2-phenylpyridine,[3] acetanilide,[4] aryl ketone
oximes,[5] azobenzene,[6] and N-nitrosoanilines[7] has been re-
ported. Acylating reagents, including α-oxo carboxylic acids,[8]
toluene,[9] benzaldehyde,[10] benzyl alcohols,[11] and aniline[12]
have been employed for this purpose. Amongst the various di-
recting groups, the 1,2,3-triazole ring system is one of the least
explored in a regioselective C–H bond activation.[13] Most of
the studies that involve N-aryl-1,2,3-triazole functionalizations,
including alkoxylations,[14] halogenations,[15] and aryl-
ations[16] have been reported by the Kuang group. Recently, the
same group also reported the acylation of these triazoles by
using toluene and benzaldehyde as the acylating reagents
along with 1,2-dichloroethane (DCE) as the solvent.[17]
Although Pd-catalyzed acylations in organic media have
been explored, there are few reports in which the reaction was
achieved in water.[11c,18] Water can serve as an ideal green sol-
vent in terms of its availability, cost, and nontoxicity, and it has
been successfully employed in various C–H bond transforma-
tions in the past few years.[19] Although reactions in water can
suffer from the low solubility of the organic substrates, this
drawback has, to an extent, been overcome by using phase-
transfer catalysts and surfactants. In our endeavor towards the
development of water as a green reaction medium, we at-
Scheme 1. Comparisons between approaches for the palladium-catalyzed
acylation of N-aryl-1,2,3-triazoles. TBHP = tert-butyl hydroperoxide.
Results and Discussion
Our investigation began with the reaction of N-phenyl-1,2,3-
triazole (1a) with benzyl alcohol (2a) in the presence of palla-
dium acetate and tert-butyl hydroperoxide (70 % in water) un-
der air at 80 °C for 24 h. We were pleased to see that a regio-
selective ortho-acylation of 1a occurred to give (phenyl)[2-(2H-
1,2,3-triazol-2-yl)phenyl]methanone (3a) as the only product in
34 % yield (Table 1, Entry 1). To improve the reaction, we pur-
sued extensive optimization studies with regard to the catalyst,
solvent, oxidant, temperature, and time by using 1a and 2a as
the model substrates (Table 1). To examine the role of palla-
[a] Department of Chemistry, Indian Institute of Technology,
New Delhi 110016 India
E-mail: njain@chemistry.iitd.ac.in
http://web.iitd.ac.in/~njain/#/home
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejoc.201600479.
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dium as the catalyst, we varied the catalytic loading of palla- creasing the amount of TBHP to 1 equiv. resulted in a decreased
dium acetate and found that increasing the amount of catalyst yield of 15 % (Table 1, Entry 15), whereas increasing the amount
from 5 to 10 mol-% improved the yield of 3a to 71 % (Table 1, to 10 equiv. resulted in the formation of a diacylated product
Entry 2). A further increase, however, in the amount of Pd(OAc)2 (Table 1, Entry 16). A variation in the reaction temperature re-
to 15 mol-% did not influence product yield (Table 1, Entry 3). vealed that lowering it to 60 °C reduced the product yield, and
As expected, in the absence of the Pd catalyst, the desired prod- increasing the temperature to 110 °C gave equally unfavorable
uct 3a did not form (Table 1, Entry 4). The screening of other results, as a large amount of unidentified impurities were
palladium salts such as PdCl2 and Pd(CH3CN)2 showed them to formed (Table 1, Entries 17 and 18). In addition, decreasing the
be less effective catalysts than Pd(OAc)2 (Table 1, Entries 5 and reaction time afforded a lower product yield, whereas extend-
6).
ing the time did not have an influence (Table 1, Entry 19 vs.
11). Notably, no trace amounts of the diacylated product were
observed after a reaction time of 24 h. Thus, the optimized
conditions included 10 mol-% of Pd(OAc)2 and 4.0 equiv. of
TBHP in H2O at 80 °C for 12 h (Table 1, Entry 11).
Table 1. Optimization of the reaction conditions for the acylation of N-aryl-
1,2,3-triazole.[a]
With the optimized conditions in hand, we investigated the
scope of reaction by varying the benzyl alcohol and N-aryl-
1,2,3-triazole substrates (Scheme 2). It was found that the reac-
tion was quite general, and a variety of benzyl alcohols were
Entry
Catalyst
(mol-%)
Oxidant
(equiv.)
Solvent
T
[°C]
Yield[b]
[%]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Pd(OAc)2 (5)
Pd(OAc)2 (10)
Pd(OAc)2 (15)
–
TBHP (4)
TBHP (4)
TBHP (4)
TBHP (4)
TBHP (4)
TBHP (4)
TBHP (4)
TBHP (4)
TBHP (4)
TBHP (4)
TBHP (4)
H2O2 (4)
K2S2O8 (4)
O2
–
–
–
–
–
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
60
110
80
34
71, 0[c]
72
–
51
63
47
55
trace
trace
84
trace
–
PdCl2 (10)
Pd(CH3CN)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
Pd(OAc)2 (10)
–
DCE
dioxane
DMF
DMSO
H2O
–
–
–
–
–
H2O
H2O
H2O
–
TBHP (1)
TBHP (10)
TBHP (4)
TBHP (4)
TBHP (4)
15
80[d]
59
45
49[e], 85[f]
[a] Reagents and conditions: 1a (0.344 mmol), 2a (0.689 mmol), Pd catalyst,
and oxidant (1.376 mmol) in H2O (0.5 mL) were heated for 12 h. [b] Isolated
yields are reported. [c] Tetra-n-butylammonium bromide (TBAB) was used as
phase-transfer catalyst (PTC). [d] Yield of diacylated product. [e] Reaction time
was 7 h. [f] Reaction time was 24 h.
Next we carried out the optimization experiments with re-
spect to the solvent. The employment of solvents such as DCE
and 1,4-dioxane decreased the product yields to 47 and 55 %,
respectively (Table 1, Entries 7 and 8), whereas the use of N,N-
dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) had
a much stronger effect on the result of the reaction, and no
product could be isolated in either case (Table 1, Entries 9 and
10). The addition of water, however, had a favorable effect and
substantially enhanced the yield of 3a to 84 % (Table 1, En-
try 11). This suggests that water is an ideal choice as a “green”
solvent for this reaction. The screenings of other oxidants such
as H2O2, K2S2O8, and O2 were then carried out, but all were
found to be ineffective, as the desired product was not ob-
tained (Table 1, Entries 12–14). Next, we optimized the reaction
for the amount of TBHP (70 % in H2O). It was found that de-
Scheme 2. Examination of the scope of the benzyl alcohol and triazole sub-
strates. Reagents and conditions: 1 (1 equiv.), 2 (2 equiv.), Pd(OAc)2 (10 mol-
%), and TBHP (4 equiv.) in H2O (0.5 mL) at 80 °C for 12 h. The isolated yields
are reported.
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well tolerated. Those benzyl alcohols that contain electron-
donating groups (i.e., OMe, Me), irrespective of whether they
are at the ortho, meta, or para position, gave excellent yields of
the corresponding products (e.g., 3b, 3c, 3m–3o). Those that
contain electron-withdrawing groups such as F, Cl, Br, and CF3
were also compatible under the reaction conditions and also
afforded reasonable product yields (e.g., 3d–3h). The N-aryl-
1,2,3-triazoles that have methyl, Cl, and F substituents at differ-
ent positions also showed a high level of regioselectivity, and
the acylations were found to occur at the sterically less hin-
dered ortho-C–H bond of the substituted N-aryl-1,2,3-triazoles
(e.g., to give 3i–3k, 3l–3p, and 3q–3v). The lowest yields were
also observed by using fluoro-substituted substrates, both in
the case of the benzyl alcohol as well as the triazole (e.g., to
give 3f, 3s, and 3v). The scope of the substrates was further
extended to aliphatic alcohols. In this case, acylation took place
smoothly irrespective of the chain length to yield 3w and 3x,
albeit in moderate yields. These lower yields may be attributed
to the reduced stability of the acyl radical, relative to a benzoyl
radical that is generated during the reaction. Unsaturated ali-
phatic alcohols, however, did not yield an acylated product. N-
Aryltriazoles that contain 3,5- and 4,5-disubstituted aryl rings
were also examined and found to afford the desired C-2-
benzoylated products 3y and 3z in 64 and 67 % yield, respec-
tively.
Scheme 3. Scope of heteroaryl alcohols as substrates. Reagents and condi-
tions: 1 (1.0 equiv.), 4 (2.0 equiv.), Pd(OAc)2 (10 mol-%), and TBHP (4.0 equiv.),
in H2O (0.5 mL) at 80 °C for 12 h. Isolated yields are reported.
In addition, methyl alcohols that are substituted with hetero-
aromatic units such as a furan or thiophene moiety also toler-
ated the reaction conditions. In these cases, the corresponding
heteroaryl ketone derivatives 5a–5g were afforded in moderate
yields (Scheme 3). An N-aryl-1,2,3-triazole that is substituted
with a chloro group at either the meta or para position showed
a high level of regioselectivity, and acylation took place at the
sterically less hindered ortho position (i.e., to give 5e, 5f, and
5g), as was also observed with the benzyl alcohols. A slightly
lower yield was obtained when furan-3-ylmethanol was used as
the substrate (i.e., to give 5d). When pyridin-3-ylmethanol was
used as the substrate, no reaction took place. The structure of
5f was confirmed by X-ray crystal structure analysis (Figure 1).
Next, this strategy was applied to the synthesis of triazole-
substituted fluorenone, which is known to be a core structural
unit of many biologically potent compounds. Traditional strate-
gies for the synthesis of fluorenone employ Friedel–Crafts ring-
closing reactions of biarylcarboxylic acids,[22] the carbonylation
of o-halobiaryls,[23] and the palladium-catalyzed cyclization of
o-iodobenzophenones.[24] By using our method, (2-bromo-
phenyl)[5-methyl-2-(2H-1,2,3-triazol-2-yl)phenyl]methanone (8)
Figure 1. Single crystal X-ray structure of 5f.
yielded 4-methyl-1-(2H-1,2,3-triazol-2-yl)-9H-fluoren-9-one (9) in
78 % yield (Scheme 4). The reaction was also performed on a
gram scale (2 g) to afford 1.20 g of the desired product (Sup-
porting Information).
Mechanism
was prepared, which upon treatment with Pd(OAc)2 and K2CO3 On the basis of reports in the literature[17,11a] and control exper-
in N,N-dimethylacetamide (DMA) as the solvent at 100 °C iments, we have proposed a plausible mechanism (Scheme 5).
Scheme 4. Synthesis of 1,2,3-triazole-substituted fluorenone.
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Scheme 5. Proposed Mechanism.
The reaction is initiated through an ortho-carbopalladation of triazole-substituted aryl, heteroaryl, and aliphatic ketones, re-
2-aryl-1,2,3-triazole (1a) with Pd(OAc)2 to form the intermediate spectively, in moderate to high yields with excellent regioselect-
A,[25] which undergoes a reaction with acyl radical B that is ivity. The reaction is effective in the absence of a PTC or surfac-
generated in situ from benzyl alcohol under oxidizing condi- tant. The procedure involves an easy workup process that em-
tions. Acyl radical B undergoes an oxidative addition to then ploys a minimal amount of organic solvent to extract the prod-
give intermediate C. Finally, a reductive elimination releases the uct from the aqueous reaction mixture, thus making the overall
desired acylated product 3a along with the regeneration of the method highly economical and environmentally friendly.
active PdII catalyst. The in situ formation of benzaldehyde as an
intermediate was confirmed by 1H NMR analysis of the reaction
mixture after 6 h of reaction time and showed the characteristic
Experimental Section
General Methods: All reactions were carried out under air in an
oven-dried round-bottomed flask that was sealed with a septum or
a sealed tube. All of the solvents were purchased from Aldrich or
Spectrochem and used as received. Palladium(II) acetate was pur-
chased from Alfa-Aesar (98 % purity). For column chromatography,
silica gel (230–400 mesh) from SRL Co. was used. A gradient elution
(ethyl acetate/hexane) was used for TLC, which was performed on
Merck aluminium sheets (silica gel 60F254). All of the isolated com-
pounds were characterized by 1H and 13C NMR spectroscopy along
aldehyde proton peak at δ = 9.8 ppm.
Interestingly, we also found that a decarboxylative acylation
of N-aryl-1,2,3-triazoles could be achieved with α-oxo acid 10
in water. After a few optimization experiments, we successfully
obtained the desired products 3a, 3u, and 3y in moderate
yields by using ammonium peroxodisulfate as the oxidant
(Scheme 6).[26]
1
with HRMS. The H and 13C NMR spectroscopic data were recorded
with a Bruker DPX-300 MHz spectrometer at 300 and 75 MHz, re-
spectively. CDCl3 and [D6]DMSO were used as the NMR solvents
with tetramethylsilane (TMS) as the internal standard at room tem-
perature. Chemical shifts are reported in δ (ppm) values relative to
that of TMS (δ = 0.00 ppm), and the coupling constants (J) are
reported in Hz. High-resolution mass spectra were recorded with a
Q-TOF (Q = quadrupole) instrument by using electrospray ioniza-
tion.
Scheme 6. Acylation of N-aryl-1,2,3-triazole with oxocarboxylic acid. Reagents
and conditions: 1 (1.0 equiv.), 10 (1.5 equiv.), Pd(OAc)2 (10 mol-%), and
(NH4)2S2O8 (2.5 equiv.), in H2O (0.5 mL) at 70 °C for 12 h. [a] Isolated yields.
General Procedure for the Preparation of Glyoxalbis(N-aryl-
osazones): The glyoxalbis(N-arylosazones) were prepared by using
a literature method.[27] To a 40 % aqueous solution of glyoxal
(5 mmol) was added phenylhydrazine (10 mmol) in ethanol (40 mL)
as the mixture was stirred and cooled in an ice bath. A yellow solid
formed instantaneously, and this yellow suspension was stirred at
room temperature for 1 h. The reaction mixture was extracted with
dichloromethane, and the organic layer was concentrated and then
dried with a vacuum pump for 45 min. The crude glyoxalbis(N-
Conclusions
We have developed an efficient and mild method for the acyl-
ation of triazoles that have pharmaceutical potential. The reac-
tion uses readily available benzylic, heterocyclic, and aliphatic
alcohols with Pd(OAc)2 and TBHP in water to yield N-aryl-1,2,3- phenyl)osazone was used directly in the next step.
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Preparation of N-Aryl-1,2,3-Triazoles: All of the triazoles were syn-
thesized by using a reported procedure.[27] An oven-dried two-neck
round-bottomed flask was charged with a mixture of the glyox-
albis(N-phenylosazone) (1 g, 0.042 mmol) and copper triflate
1 H), 7.62 (m, 2 H), 7.50 (d, J = 9 Hz, 2 H), 7.21 (dd, J1 = 12 Hz, J2 =
15 Hz, 3 H), 7.14 (dd, J1 = 12 Hz, J2 = 15 Hz, 1 H), 6.94 (t, J = 6 Hz,
1 H), 2.63 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 196.82, 139.76,
138.11, 137.00, 135.81, 134.54, 132.94, 132.01, 131.62, 131.43,
(0.05 g, 0.14 mmol) in dry toluene (10 mL). The contents were 130.17, 128.48, 125.96, 125.09, 123.08, 21.16 ppm. ESI-MS: calcd. for
stirred and heated at reflux under a stream of nitrogen at 110 °C
for 12 h. After this, the reaction mixture was cooled to room tem-
perature, and the solvent was evaporated under reduced pressure.
The oily residue was purified by chromatography on a silica gel
column (hexane/ethyl acetate, 98:2) to yield the desired compound.
C16H13N3O 263.0950; found 263.09211.
(3-Chlorophenyl)[2-(2H-1,2,3-triazol-2-yl)phenyl]methanone
(3d): Brown solid (82 mg, 82 %). 1H NMR (400 MHz, CDCl3): δ = 8.03
(d, J = 8.1 Hz, 1 H), 7.70 (m, 2 H), 7.56 (s, J = 8.1 Hz, 4 H), 7.47 (d,
J = 6 Hz, 1 H), 7.41 (dd, J = 5.1 Hz, 1 H), 7.24 (dd, J1 = 7.5 Hz, J2 =
13.2 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 193.78, 138.71,
137.63, 135.94, 134.60, 132.74, 131.87, 131.43, 129.56, 129.53,
128.75, 128.29, 127.07, 122.30 ppm. ESI-MS: calcd. for
Typical Procedure for the ortho-Acylation of N-Aryl-1,2,3-tri-
azoles To Yield 3a–3z and 5a–5g: An oven-dried reaction vessel
was charged with a mixture of N-aryl-1,2,3-triazole (1, 0.34 mmol),
the benzyl alcohol (2, 0.68 mmol, 2 equiv.), Pd(OAc)2 (0.0344 mmol,
10 mol-%), TBHP (1.36 mmol, 4 equiv.), and H2O (0.5 mL) at room
temperature, and the system was sealed with a Teflon cap. The
contents were stirred at 80 °C for 12 h and then cooled to room
temperature. A slurry was made by adding silica gel directly into
the reaction mixture. The residue was purified by column chroma-
tography on silica gel (hexane/ethyl acetate, 93:7) to yield the ortho-
acylated 2-aryl-1,2,3-triazole as the product.
C15H10ClN3ONa 306.0404; found 306.0406.
(4-Chlorophenyl)[2-(2H-1,2,3-triazol-2-yl)phenyl]methanone
(3e):[17b] Pale yellow liquid (83 mg, 83 %). 1H NMR (400 MHz, CDCl3):
δ = 8.01 (d, J = 6.0 Hz, 1 H), 7.66 (ddd, J1 = 1.8 Hz, J2 = 5.1 Hz, J3 =
11.4 Hz, 1 H), 7.60 (d, J = 6.6 Hz, 2 H), 7.55 (d, J = 3.3 Hz, 4 H), 7.28
(d, J = 6.6 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 193.92,
139.20, 137.59, 135.93, 135.79, 135.52, 131.28, 130.27, 129.56,
128.98, 128.60, 128.24, 122.28 ppm. ESI-MS: calcd. for C15H10ClN3O
283.0512; found 283.0833.
Procedure for the ortho-Acylation of N-Aryl-1,2,3-triazoles by
α-Oxocarboxylic Acid To Yield 3a, 3u, and 3y: An oven-dried re-
action vessel was charged with a mixture of N-aryl-1,2,3-triazole (1,
0.34 mmol), 2-oxo-2-phenylacetic acid (10, 0.51 mmol, 1.5 equiv.),
Pd(OAc)2 (0.0344 mmol, 10 mol-%), ammonium peroxodisulfate
(NH4)2S2O8 (0.85 mmol, 2.5 equiv.), and H2O (0.5 mL) at room tem-
perature, and the system was sealed with a Teflon cap. The contents
were stirred at 80 °C for 12 h and then cooled to room temperature.
A slurry was made by adding silica gel directly into the reaction
mixture. The residue was purified by column chromatography on
silica gel (hexane/ethyl acetate, 93:7) to yield the ortho-acylated 2-
aryl-1,2,3-triazoles as the product.
(4-Fluorophenyl)[2-(2H-1,2,3-triazol-2-yl)phenyl]methanone
1
(3f):[17b] Brown solid (66 mg, 66 %). H NMR (400 MHz, CDCl3): δ =
8.14 (dd, J1 = 5.1 Hz, J2 = 5.7 Hz, 1 H), 7.99 (d, J = 6 Hz, 1 H), 7.65
(m, 3 H), 7.54 (d, J = 1.8 Hz, 2 H), 7.13 (t, J = 6.3 Hz, 1 H), 6.94 (t,
J = 1.5 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 193.67, 167.18
(1JC,F = 250.5 Hz), 137.59, 135.89, 133.52, 132.89, 132.35, 131.60,
131.20, 129.48, 128.30, 122.37, 115.57 (2JC,F = 21.7 Hz) ppm. ESI-MS:
calcd. for C15H10FN3OH+ 268.0881; found 268.0147.
[2-(2H-1,2,3-Triazol-2-yl)phenyl][4-(trifluoromethyl)phenyl]-
methanone (3g):[17b] White solid (71 mg, 71 %). 1H NMR (400 MHz,
CDCl3): δ = 8.04 (d, J = 6 Hz, 1 H), 7.76 (d, J = 6 Hz, 2 H), 7.68 (dt,
J = 6 Hz, 1 H), 7.56 (s, 3 H), 7.53 (d, J = 4.8 Hz, 3 H) ppm. 13C NMR
Synthesis of 4-Methyl-1-(2H-1,2,3-triazol-2-yl)-9H-fluoren-9-one
(9):[28] To a 15 mL vial that contained (2-bromophenyl)[5-methyl-
2-(2H-1,2,3-triazol-2-yl)phenyl]methanone (8, 5.86 mmol), Pd(OAc)2
(3 mol-%), 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (BINAP,
10 mol-%), K2CO3 (3 equiv.), and trimethylacetic acid (0.5 mmol)
was added DMA (5 mL). The resulting mixture was heated at 120 °C
for 8 h. After cooling to room temperature, water was added, and
the product was extracted with ethyl acetate (6 × 20 mL). The or-
ganic layer was concentrated under reduced pressure. Column chro-
matography on silica gel (hexane/ethyl acetate, 95:5) gave the de-
sired product.
(75 MHz, CDCl3): δ = 193.95, 139.95, 137.69, 135.97, 134.61 (2JC,F
=
32.4 Hz), 131.57, 129.57, 129.08, 128.35, 125.30 (3JC,F = 3.8 Hz),
122.26 (1JC,F = 271.5 Hz) ppm. ESI-MS: calcd. for C16H10F3N3O
317.0776; found 317.0864.
(2-Bromophenyl)[2-(2H-1,2,3-triazol-2-yl)phenyl]methanone
(3h):[17b] Pale yellow solid (81 mg, 73 %). 1H NMR (400 MHz, CDCl3):
δ = 7.79 (d, J = 6 Hz, 1 H), 7.63 (dd, J1 = 5.7 Hz, J2 = 8.7 Hz, 2 H),
7.49 (d, J = 3.3 Hz, 3 H), 7.46 (d, J = 5.1 Hz, 1 H), 7.18 (dd, J1
=
1.5 Hz, J2 = 5.4 Hz, 1 H), 7.08 (m, 2 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 193.67, 138.36, 138.19, 135.90, 134.33, 133.68, 132.19,
132.07, 131.03, 130.67, 130.19, 128.84, 126.57, 123.33, 121.68 ppm.
ESI-MS: calcd. for C15H10BrN3O 327.0007; found 327.1589.
Spectral Data
(Phenyl)[2-(2H-1,2,3-triazol-2-yl)phenyl]methanone
(3a):[17b]
Yellowish brown solid (70 mg, 84 %). 1H NMR (300 MHz, CDCl3): δ =
7.90 (d, J = 8.1 Hz, 1 H), 7.55 (d, J = 7.2 Hz, 3 H), 7.41 (d, 4 H, d =
8.7 Hz), 7.32 (d, J = 7.5 Hz, 1 H), 7.18 (t, J = 7.5 Hz, 2 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 195.16, 137.70, 137.02, 135.83, 132.86,
132.68, 131.07, 129.56, 128.98, 128.27, 128.22 ppm. ESI-MS: calcd.
for C15H11N3OH+ 250.0975; found 250.0367.
(4-Chlorophenyl)[5-methyl-2-(2H-1,2,3-triazol-2-yl)phenyl]-
methanone (3i): White solid (75 mg, 81 %). 1H NMR (400 MHz,
CDCl3): δ = 7.85 (d, J = 6.3 Hz, 1 H), 7.55 (d, J = 5.1 Hz, 2 H), 7.50
(s, 2 H), 7.46 (dd, J1 = 0.9 Hz, J2 = 6.3 Hz, 1 H), 7.33 (1 H), 7.25 (d,
J = 5.1 Hz, 2 H), 2.44 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
194.13, 139.12, 138.65, 135.68, 135.54, 135.48, 132.00, 131.92,
130.24, 129.83, 128.55, 122.24, 21.02 ppm. ESI-MS: calcd. for
(4-Methoxyphenyl)[2-(2H-1,2,3-triazol-2-yl)phenyl]methanone
(3b): Brown solid (80 mg, 88 %). 1H NMR (300 MHz, CDCl3): δ = 8.00 C16H12ClN3O 297.0669; found 297.0478.
(d, J = 7.5 Hz, 1 H), 7.62 (d, J = 7.5 Hz, 1 H), 7.55 (s, 4 H), 7.33 (s, 1
(3-Chlorophenyl)[5-methyl-2-(2H-1,2,3-triazol-2-yl)phenyl]-
H), 7.11 (m, 2 H), 7.00 (d, J = 7.2 Hz, 1 H), 3.8 (s, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 194.34, 159.57, 138.36, 135.82, 132.69, 131.04,
129.55, 129.21, 128.15, 122.27, 122.08, 119.78, 112.65, 55.37 ppm.
ESI-MS: calcd. for C16H13N3O2H+ 280.1081; found 280.0275.
methanone (3j): Reddish brown liquid (78 mg, 78 %). 1H NMR
(300 MHz, CDCl3): δ = 7.90 (d, J = 7.5 Hz, 1 H), 7.70 (s, 1 H), 7.54 (s,
2 H), 7.51 (t, J = 7.2 Hz, 2 H), 7.39 (t, J = 6 Hz, 1 H), 7.28 (dd, J1 =
8.1 Hz, J2 = 16.8 Hz, 2 H), 2.49 (s, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 194.01, 138.76, 136.61, 135.67, 134.54, 132.66, 132.06,
131.78, 131.10, 129.86, 129.50, 128.71, 127.02, 122.25, 119.14,
(o-Tolyl)[2-(2H-1,2,3-triazol-2-yl)phenyl]methanone (3c):[17a] Pale
yellow solid (85 mg, 85 %). 1H NMR (300 MHz, CDCl3): δ = 7.88 (s,
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21.03 ppm. ESI-MS: calcd. for C16H12ClN3O 297.0669; found
297.0148.
[4-Chloro-2-(2H-1,2,3-triazol-2-yl)phenyl](4-chlorophenyl)-
methanone (3r): Light yellow liquid (78 mg, 78 %). 1H NMR
(300 MHz, CDCl3): δ = 7.982 (s, 1 H), 7.52 (d, J = 8.4 Hz, 4 H), 7.41
(s, 2 H), 7.22 (d, J = 8.4 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
192.90, 139.46, 138.28, 137.16, 136.31, 135.33, 130.68, 130.20,
128.71, 128.31, 123.60, 122.35 ppm. ESI-MS: calcd. for C15H9Cl2N3O,
317.0123; found 317.1543.
[5-Methyl-2-(2H-1,2,3-triazol-2-yl)phenyl](o-tolyl)methanone
(3k): Brown solid (85 mg, 85 %). 1H NMR (400 MHz, CDCl3): δ = 7.65
(d, J = 8.7 Hz, 1 H), 7.39 (s, 2 H), 7.35 (s, 2 H), 7.15 (dd, J1 = 7.5 Hz,
J2 = 15.6 Hz, 1 H), 7.03 (t, J = 8.1 Hz, 2 H), 6.86 (t, J = 7.2 Hz, 1 H),
2.54 (s, 3 H), 2.38 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 196.82,
139.57, 138.61, 137.00, 135.94, 135.37, 134.37, 131.85, 131.41,
131.36, 130.34, 130.07, 124.89, 122.95, 21.03, 20.95 ppm. HRMS:
calcd. for C17H15N3NaO 300.1107; found 300.1109.
[4-Chloro-2-(2H-1,2,3-triazol-2-yl)phenyl](4-fluorophenyl)-
methanone (3s): Brown solid (68 mg, 68 %). 1H NMR (400 MHz,
CDCl3): δ = 8.05 (s, 1 H), 7.68 (dd, J1 = 3.9 Hz, J2 = 5.7 Hz, 2 H), 7.65
(s, 2 H), 7.49 (s, 2 H), 6.98 (t, J = 6.3 Hz, 2 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 192.60, 167.29 (d, JC,F = 253.7 Hz), 163.90, 138.29, 137.06,
[4-Methyl-2-(2H-1,2,3-triazol-2-yl)phenyl](phenyl)methanone
1
(3l): Brown solid (83 mg, 83 %). H NMR (400 MHz, CDCl3): δ = 7.78
136.27, 133.32, 131.57, 130.67, 128.30, 122.42, 115.70 (d, JC,F
=
(s, 1 H), 7.65 (d, J = 5.4 Hz, 2 H), 7.51 (s, 2 H), 7.49 (d, J = 6 Hz, 1 H),
7.43 (t, J = 5.4 Hz, 1 H), 7.34 (d, J = 5.7 Hz, 1 H), 7.27 (t, J = 5.7 Hz,
2 H), 2.52 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 195.35, 141.94,
137.78, 137.23, 135.70, 133.61, 132.69, 130.15, 129.72, 128.93,
128.44, 128.17, 122.95, 21.39 ppm. HRMS: calcd. for C16H13N3NaO
286.0950; found 286.0949.
21.9 Hz) ppm. HRMS: calcd. for C15H9ClFN3NaO 324.03102; found
324.03103.
[4-Chloro-2-(2H-1,2,3-triazol-2-yl)phenyl](o-tolyl)methanone
(3t): Pale yellow liquid (77 mg, 77 %). 1H NMR (400 MHz, CDCl3):
δ = 7.86 (s, 1 H), 7.43 (m, 4 H), 7.61 (t, J = 9 Hz, 1 H), 7.09 (d, J =
7.2 Hz, 1 H), 7.02 (d, J = 7.5 Hz, 1 H), 6.89 (t, J = 7.5 Hz, 1 H), 2.56
(s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 195.60, 139.79, 138.67,
137.07, 136.64, 136.03, 132.54, 131.66, 131.59, 131.21, 129.94,
128.34, 125.02, 123.06, 20.98 ppm. ESI-MS: calcd. for C16H12ClN3O
297.0669; found 297.0478.
(2,5-Dimethoxyphenyl)[4-methyl-2-(2H-1,2,3-triazol-2-yl)phen-
1
yl]methanone (3m): White solid (88 mg, 89 %). H NMR (400 MHz,
CDCl3): δ = 7.77 (s, 1 H), 7.56 (s, 2 H), 7.48 (dd, J1 = 5.7 Hz, J2
=
9.3 Hz, 2 H), 7.33 (d, J = 5.4 Hz, 1 H), 7.09 (dd, J1 = 3 Hz, J2 = 6 Hz,
1 H), 6.67 (d, J = 6.3 Hz, 1 H), 3.88 (s, 3 H), 3.86 (s, 3 H), 2.51 (s, 3 H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 194.02, 153.06, 148.86, 141.53,
137.67, 135.69, 135.47, 130.37, 129.60, 128.92, 124.49, 124.31,
123.00, 121.81 110.63, 109.71, 55.94, 21.35 ppm. HRMS: calcd. for
[4-Chloro-2-(2H-1,2,3-triazol-2-yl)phenyl](phenyl)methanone
(3u): Pale yellow solid (78 mg, 79 %). 1H NMR (400 MHz, CDCl3): δ =
8.04 (s, 1 H), 7.63 (d, J = 8.4 Hz, 2 H), 7.53 (s, 2 H), 7.49 (s, 2 H), 7.44
(d, J = 7.2 Hz, 1 H), 7.33 (d, J = 7.8 Hz, 2 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 194.15, 138.39, 136.88, 136.84, 136.20, 133.03, 130.78,
128.94, 128.36, 128.22, 122.36 ppm. HRMS: calcd. for C15H10ClKN3O
322.0143; found 322.0143.
C
18H17N3NaO3 346.1153; found 346.1154.
(4-Methoxyphenyl)[4-methyl-2-(2H-1,2,3-triazol-2-yl)phenyl]-
methanone (3n): Brown liquid (87 mg, 88 %). 1H NMR (400 MHz,
CDCl3): δ = 7.72 (s, 1 H), 7.65 (d, J = 6.6 Hz, 2 H), 7.55 (s, 2 H), 7.44
(d, J = 5.7 Hz, 1 H), 7.32 (d, J = 5.7 Hz, 1 H), 6.78 (d, J = 6.6 Hz, 2
H), 3.80 (s, 3 H), 2.51 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
194.04, 163.26, 141.44, 137.68, 135.62, 131.34, 130.52, 130.34,
129.50, 128.88, 122.97, 113.47, 55.37, 21.34 ppm. HRMS: calcd. for
C17H15N3NaO2 316.1055; found 316.1056.
[5-Fluoro-2-(2H-1,2,3-triazol-2-yl)phenyl](4-methoxyphenyl)-
methanone (3v): Pale yellow solid (69 mg, 69 %). 1H NMR
(400 MHz, CDCl3): δ = 7.96 (dd, J1 = 3.6 Hz, J2 = 6.9 Hz, 1 H), 7.66
(d, J = 5.4 Hz, 2 H), 7.56 (s, 2 H), 7.33 (dt, J = 2.1 Hz, 1 H), 7.25 (dd,
J1 = 2.1 Hz, J2 = 6 Hz, 1 H), 6.81 (d, J = 6.6 Hz, 2 H), 3.81 (s, 3 H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 192.20, 163.65, 163.37 (d, JC,F
=
250.72), 135.83, 135.07, 133.88, 133.88, 131.47, 129.41, 124.64,
117.80, 116.52 (d, JC,F = 24.15 Hz), 113.69, 55.43 ppm. ESI-MS: calcd.
for C16H12FN3O2 297.0914; found 298.0807.
[4-Methyl-2-(2H-1,2,3-triazol-2-yl)phenyl](o-tolyl)methanone
(3o): Pale yellow solid (80 mg, 81 %). 1H NMR (300 MHz, CDCl3): δ =
7.59 (s, 1 H), 7.46 (d, J = 7.8 Hz, 1 H), 7.41 (d, J = 6 Hz, 2 H), 7.27 (d,
J = 7.5 Hz, 1 H), 7.12 (d, J = 6.9 Hz, 1 H), 7.06 (dd, J1 = 7.2 Hz, J2 =
11.1 Hz, 2 H), 6.86 (t, J = 7.2 Hz, 1 H), 2.51 (s, 3 H), 2.43 (s, 3 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 195.76, 143.89, 142.20, 139.40, 138.15,
137.51, 135.51, 131.91, 131.34, 130.19, 129.82, 129.10, 124.85,
123.67, 21.37, 20.86 ppm. ESI-MS: calcd. for C17H15N3O 277.1215;
found 277.1470.
1-[2-(2H-1,2,3-Triazol-2-yl)phenyl]ethanone (3w):[17b] Brown liq-
1
uid (60 mg, 60 %). H NMR (400 MHz, CDCl3): δ = 7.84 (t, J = 3 Hz,
3 H), 7.54 (dd, J1 = 8.4 Hz, J2 = 6.3 Hz, 2 H), 7.45 (d, J = 1.8 Hz, 1
H), 2.19 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 199.89, 136.43,
136.16, 134.27, 133.03, 130.97, 127.90, 127.20, 30.10 ppm. ESI-MS:
calcd. for C10H8N3NaO 209.0565; found 209.0240.
(4-Chlorophenyl)[4-methyl-2-(2H-1,2,3-triazol-2-yl)phenyl]-
methanone (3p): Pale yellow solid (81 mg, 82 %). 1H NMR
(300 MHz, CDCl3): δ = 7.80 (s, 1 H), 7.54 (t, J = 6 Hz, 4 H), 7.46 (d,
J = 7.8 Hz, 1 H), 7.33 (d, J = 7.5 Hz, 1 H), 7.27 (d, J = 8.4 Hz, 2 H),
2.52 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 193.97, 142.18,
138.98, 137.66, 135.80, 133.61, 131.51, 130.18, 129.62, 129.07,
128.81, 128.49, 122.88, 21.39 ppm. HRMS: calcd. for C16H12ClN3ONa
320.0558; found 320.0559.
1-[2-(2H-1,2,3-Triazol-2-yl)phenyl]butan-1-one (3x): Yellow solid
(62 mg, 62 %). H NMR (300 MHz, CDCl3): δ = 7.90 (d, J = 8.7 Hz, 1
1
H), 7.83 (s, 2 H), 7.534 (dd, J1 = 2.1 Hz, J2 = 2.4 Hz, 2 H), 7.40 (d, J =
2.1 Hz, 1 H), 2.42 (t, J = 7.2 Hz, 2 H), 1.68 (q, J1 = 7.2 Hz, J2 = 10.2 Hz,
2 H), 0.89 (t, J = 5.4 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
202.77, 136.25, 134.99, 134.07, 133.60, 127.80, 123.77, 44.85, 29.70,
17.57, 13.63 ppm. ESI-MS: calcd. for C12H13N3NaO 238.0956; found
238.2899.
[4-Chloro-2-(2H-1,2,3-triazol-2-yl)phenyl](m-tolyl)methanone
(3q): Pale yellow solid (80 mg, 80 %). 1H NMR (300 MHz, CDCl3): δ =
7.71 (s, 1 H), 7.58 (m, 2 H), 7.45 (s, 2 H), 7.40 (d, J = 7.8 Hz, 1 H),
7.27 (d, J = 7.8 Hz, 1 H), 6.87 (t, J = 8.4 Hz, 2 H), 2.44 (s, 3 H) ppm.
[4,5-Dimethyl-2-(2H-1,2,3-triazol-2-yl)phenyl](phenyl)methan-
one (3y): White solid (64 mg, 64 %). 1H NMR (300 MHz, CDCl3): δ =
7.74 (s, 1 H), 7.69 (d, J = 7.2, 2 H), 7.53 (s, 2 H), 7.44 (t, J = 7.2 Hz, 1
H), 7.36 (s, 1 H), 7.28 (t, J = 7.8 Hz, 2 H), 2.43 (s, 3 H), 2.38 (s, 3 H)
13C NMR (75 MHz, CDCl3): δ = 193.68, 167.07, 163.69, 142.04, 137.70, ppm. 13C NMR (75 MHz, CDCl3): δ = 195.36, 140.37, 137.35, 137.21,
135.73, 133.77, 131.49, 131.37, 129.80, 129.59, 129.05, 122.96,
135.81, 135.42, 132.55, 130.58, 130.27, 128.89, 128.39, 128.10,
115.45, 115.16, 21.37 ppm. HRMS: calcd. for C16H12ClN3NaO 123.38, 19.82, 19.34 ppm. HRMS: calcd. for C17H15N3NaO 300.1107;
320.0556; found 320.0561.
found 300.1108.
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[2,4-Dimethyl-6-(2H-1,2,3-triazol-2-yl)phenyl](phenyl)methan-
one (3z): Pale yellow liquid (67 mg, 67 %). 1H NMR (300 MHz,
4-Methyl-1-(2H-1,2,3-triazol-2-yl)-9H-fluoren-9-one (9): Yellow
solid (1.20 g, 78 %). 1H NMR (300 MHz, CDCl3): δ = 7.91 (s, 1 H), 7.71
CDCl3): δ = 7.70 (d, J = 4.8 Hz, 1 H), 7.50 (s, 2 H), 7.44 (t, J1 = 6 Hz, (dd, J1 = 7.8 Hz, J2 = 13.2 Hz, 2 H), 7.55 (s, J = 7.5 Hz, 1 H), 7.38 (d,
1 H), 7.33 (dd, J1 = 7.8 Hz, J2 = 15 Hz, 2 H), 7.14 (s, 1 H), 2.53 (s, 3
J = 2.7 Hz, 2 H), 7.34 (s, J = 8.1 Hz, 1 H), 2.67 (s, 3 H) ppm. 13C NMR
H), 2.27 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 195.35, 140.15, (75 MHz, CDCl3): δ = 189.93, 143.79, 143.52, 137.89, 135.64, 134.66,
137.68, 137.38, 137.25, 135.29, 132.84, 131.09, 129.18, 128.72,
128.34, 119.98, 19.81, 19.34 ppm. HRMS: calcd. for C17H15N3NaO
300.1101; found 300.1102.
134.51, 134.33, 129.11, 126.87, 125.88, 124.60, 123.55, 20.45 ppm.
HRMS: calcd. for C16H11N3NaO 284.0794; found 284.0792.
Supporting Information (see footnote on the first page of this
article): Spectroscopic (1H NMR and 13C NMR) and EI-MS data for
the synthesized compounds.
(Thiophen-2-yl)[2-(2H-1,2,3-triazol-2-yl)phenyl]methanone (5a):
1
Brown solid (76 mg, 76 %). H NMR (400 MHz, CDCl3): δ = 8.00 (d,
J = 6.3 Hz, 1 H), 7.64 (m, 4 H), 7.53 (t, J = 5.4 Hz, 1 H), 7.44 (s, 1 H),
6.83 (d, J = 2.1 Hz, 1 H), 6.36 (d, J = 1.5 Hz, 1 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 182.38, 152.45, 146.84, 137.73, 135.86, 131.78,
131.44, 129.60, 128.08, 122.49, 118.45, 112.09 ppm. HRMS: calcd. for
C13H9N3NaOS 278.0358; found 278.0335.
Acknowledgments
This work has been financially supported by the Council of Sci-
entific and Industrial Research (CSIR), India (02/0180/14/EMR-II).
C. P. and S. S. P. thank the CSIR for their graduate fellowships.
The authors thank the Department of Science and Technology
– Fund for Improvement of Science and Technology (DST-FIST)
for funding the ESI-HRMS facility at the Indian Institute of Tech-
nology (IIT) Delhi.
(Furan-2-yl)[2-(2H-1,2,3-triazol-2-yl)phenyl]methanone (5b):
1
Brown solid (72 mg, 73 %). H NMR (400 MHz, CDCl3): δ = 7.93 (d,
J = 6.3 Hz, 1 H), 7.57 (m, 4 H), 7.44 (ddd, J1 = 0.6 Hz, J2 = 5.7 Hz,
J3 = 11.1 Hz, 1 H), 7.36 (s, 1 H), 6.75 (d, J = 2.7 Hz, 1 H), 6.30 (dd,
J1 = 1.2 Hz, J2 = 2.7 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
182.37, 152.44, 146.84, 137.73, 135.85, 131.77, 131.43, 129.59,
128.08, 124.58, 122.48, 118.47, 112.09 ppm. HRMS: calcd. for
C13H9N3NaO2 262.0586; found 262.0584.
Keywords: Acylation · Nitrogen heterocycles · C–H
(5-Methylfuran-2-yl)[2-(2H-1,2,3-triazol-2-yl)phenyl]methanone
(5c): Yellow solid (78 mg, 79 %). 1H NMR (400 MHz, CDCl3): δ = 7.94
(d, J = 6.6 Hz, 1 H), 7.66 (s, 2 H), 7.59 (d, J = 1.8 Hz, 2 H), 7.58 (s, J =
2.7 Hz, 2 H), 6.77 (s, 1 H), 6.03 (d, J = 2.1 Hz, 1 H), 2.27 (s, 3 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 180.02, 158.86, 150.69, 136.18, 136.02,
133.93, 133.10, 131.18, 129.58, 123.94, 121.40, 109.25, 13.99 ppm.
HRMS: calcd. for C14H11N3NaO2 276.0851; found 276.0853.
activation · Regioselectivity · Palladium
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1
low solid (48 mg, 59 %). H NMR (400 MHz, CDCl3): δ = 8.01 (d, J =
1.2 Hz, 1 H), 7.70 (s, 2 H), 7.48 (m, 4 H), 7.34 (t, J = 1.2 Hz, 1 H), 6.70
(s, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 187.61, 148.27, 144.27,
137.02, 136.41, 135.94, 131.59, 130.26, 128.30, 127.82 123.01,
108.74 ppm. ESI-MS: calcd. for C13H9N3NaO2 262.0592; found
262.0584.
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methanone (5e): Brown solid (73 mg, 74 %). 1H NMR (400 MHz,
CDCl3): δ = 8.09 (s, 1 H), 7.91 (d, J = 6.3 Hz, 1 H), 7.64 (s, 2 H), 7.56
(d, J = 6.3 Hz, 1 H), 6.75 (s, 1 H), 5.01 (d, J = 2.1 Hz, 1 H), 2.25 (s, 3
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 180.05, 150.68, 149.04,
144.06, 136.03, 133.95, 133.09, 131.20, 129.58, 123.96, 109.89,
109.28, 13.98 ppm. HRMS: calcd. for C14H10ClN3NaO2 310.0128;
found 310.0129.
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δ = 7.97 (d, J = 6.6 Hz, 1 H), 7.64 (s, J = 9.3 Hz, 3 H), 7.45 (ddd, J1 =
1.8 Hz, J2 = 6.6 Hz, J3 = 13.2 Hz, 1 H), 7.44 (s, 1 H), 6.90 (d, J =
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1
anone (5g): White solid (71 mg, 71 %). H NMR (400 MHz, CDCl3):
δ = 7.97 (d, J = 6.6 Hz, 1 H), 7.65 (s, 3 H), 7.58 (ddd, J1 = 1.8 Hz, J2 =
6.3 Hz, J3 = 13.5 Hz, 1 H), 7.44 (s, 1 H), 6.89 (d, J = 2.7 Hz, 1 H), 6.40
(dd, J1 = 1.2 Hz, J2 = 2.7 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 180.76, 152.06, 147.12, 136.07, 133.96, 132.80, 131.34, 129.46,
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Received: April 16, 2016
Published Online: ■
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Full Paper
C–H Acylation
C. Premi, S. S. Patel, N. Jain* .......... 1–9
Regioselective ortho-Acylation of N-
Aryl-1,2,3-triazoles with Alcohols in
Water
A palladium-catalyzed regioselective der aqueous conditions to give the
ortho-acylation of N-aryl-1,2,3-triazoles corresponding
triazole-substituted
with benzylic, heterocyclic, and ali- ketones in moderate to high yields.
phatic alcohols has been achieved un- TBHP = tert-butyl hydroperoxide.
DOI: 10.1002/ejoc.201600479
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim