Microwave-assisted convenient synthesis of α,β-unsaturated esters and ketones via aldol-adduct elimination

Article abstract of DOI:10.1002/hlca.201200526

Various fluorinated 3-oxo ester/1,3-diketones were reacted with carbonyl compounds, in presence of piperidine and under microwave irradiation, to afford (E)-α,β-unsaturated esters and ketones in good yields. The systematic study reveals that the reaction proceeded through the formation of aldol adduct. The method provides a new and simple way for C,C bond formations. Copyright

Full text of DOI:10.1002/hlca.201200526

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Helvetica Chimica Acta – Vol. 96 (2013)
Microwave-Assisted Convenient Synthesis of a,b-Unsaturated Esters and
Ketones via Aldol-Adduct Elimination
by Pathi Suman, Rayala Nageswara Rao, and Bhimapaka China Raju*
Natural Products Chemistry Division, CSIR-Indian Institute of Chemical Technology,
Hyderabad-500 007, India
(phone: þ 914027191725; fax: þ 91402716512; e-mail: chinarajuiict@yahoo.co.in)
Various fluorinated 3-oxo ester/1,3-diketones were reacted with carbonyl compounds, in presence of
piperidine and under microwave irradiation, to afford (E)-a,b-unsaturated esters and ketones in good
yields. The systematic study reveals that the reaction proceeded through the formation of aldol adduct.
The method provides a new and simple way for C,C bond formations.
Introduction. – (E)-a,b-Unsaturated esters and ketones are important intermedi-
ates for the synthesis of natural products and biologically important heterocyclic
compounds [1]. Wittig and HornerꢀWadsworthꢀEmmons reactions are the classical
methods to produce (E)-a,b-unsaturated esters [2]. Knoevenagel condensation of non-
fluorinated 3-oxo esters with aldehydes depending on the reaction conditions resulted
in the formation of mono/dimethylene-3-oxo esters [3], whereas fluorinated 3-oxo
esters (ethyl 4,4,4-trifluoro-3-oxobutanoate) seldom lead to the (E)-3-phenyl-2-(2,2,2-
trifluoroacetyl)prop-2-enoate, and 2,6-bis(trifluoromethyl)tetrahydropyrans or 4-aryl-
(alkyl)-3,5-dialkoxycarbonyl-2,6-dihydroxy-2,6-bis(fluoroalkyl)tetrahydropyrans [4].
However, to the best of our knowledge, there is no method available in the literature
for the synthesis of (E)-a,b-unsaturated esters/ketones by the reaction of carbonyl
compounds with fluorinated 3-oxo ester/1,3-diketones such as ethyl 4,4,4-trifluoro-3-
oxobutanoate/1,1,1-trifluoropentane-2,4-dione.
Results and Discussion. – Our studies recently focused on feasible reactions of
carbonyl compounds/salicylaldehydes with 3-oxobutanoates bearing chloro or trifluoro
substituents. In this context, we studied the reactivity of salicylaldehydes with ethyl 4-
chloro-3-oxobutanoate using piperidine to provide 2H-chromenes [5], interim these
derivatives were successfully converted to corresponding 2,3-dihydrobenzoxepine-4-
carboxylates [6]. We also studied the reactivity of various carbonyl compounds with
ethyl 4,4,4-trifluoro-3-oxobutanoate using piperidine in CH2Cl2 at room temperature to
provide a series of (E)-a,b-unsaturated esters, and the established method was
successfully applied for the synthesis of variety of (E)-a,b-unsaturated ketones [7]. As
part of our program to synthesize biologically active heterocyclic compounds and
discovery of new synthetic methodologies [8], and in an extension of our previous work
[7], here, we report synthesis of (E)-a,b-unsaturated esters and ketones by the reaction
ꢀ 2013 Verlag Helvetica Chimica Acta AG, Zꢁrich

Helvetica Chimica Acta – Vol. 96 (2013)
1549
of carbonyl compounds with various oxobutanoates such as ethyl 4,4,4-trichloro-3-
oxobutanoate, 1,1,1,5,5,5-hexafluoropentane-2,4-dione, 4,4,4-trifluoro-1-(naphthalene-
2-yl)butane-1,3-dione, and 4,4,4-trifluoro-1-(furan-2-yl)butane-1,3-dione using piper-
idine in CH2Cl2 at room temperature/ under reflux conditions. Further, the method was
modified by applying microwave irradiation, and the results are presented below.
In a model reaction, 2-chloro-5-phenylnicotinaldehyde (1g; 1 mmol), ethyl 4,4,4-
trifluoro-3-oxobutanoate (2a; 1.2 mmol), and piperidine (1.2 mmol) in CH2Cl2 (4 ml)
at room temperature furnished a product (90% yield; Scheme 1), identified as ethyl
(E)-3-(2-chloro-5-phenylpyridin-3-yl)prop-2-enoate (3ze) [7], presumably via an aldol
adduct or Knoevenagel intermediate. Systematically, a series of experiments were
conducted to study the reaction mechanism, and the progress of the reactions was
1
monitored by LC/MS and H-NMR. The LC/MS data (Zorbax SB C3, 150 ꢁ 4.6 mm,
5 mm; MeCN/H2O 70 :30; 1 ml/min) indicated that the reaction proceeded through the
1
formation of aldol primary adduct (A; (4.396 min; 27%; Scheme 2). The H-NMR
experiment was carried out in an NMR tube with CDCl3, and the formed aldol adduct
was analyzed; the signal of HꢀC(2) (between the two C¼O groups of primary aldols)
appeared as doublet at d(H) 3.24 (J ¼ 11.9) and H-atom signal of the HOꢀCH group
appeared as triplet-like signal at d(H) 4.90 (J ¼ 11.9). Piperidyl H-atom signals were
detected as two separate singlets at d(H) 8.60 and 8.08. The ester Me signal appeared as
triplet at d(H) 1.24 (J ¼ 6.9), and CH2O gave rise to a quartet at d(H) 4.08 (J ¼ 6.9).
Further attack of piperidine at trifluoroacetyl C¼O C-atom of aldol primary adduct (A)
led to the intermediate B. The in situ stereoselective elimination of piperidinium
Scheme 1
Scheme 2. Proposed Mechanism for Tandem Aldol-Adduct Elimination

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Helvetica Chimica Acta – Vol. 96 (2013)
trifluoroacetate afforded (E)-a,b-unsaturated ester 3 (Scheme 2). The eliminated
piperidinium trifluoroacetate salt was analyzed by 19F- and 1H-NMR spectroscopy. The
19F-NMR spectrum exhibited a singlet at d(F) ꢀ 76.17 (Fig. 1) for piperidinium
trifluoroacetate salt, in agreement with the corresponding value of the prepared salt,
d(F) ꢀ 76.25; Fig. 21). The 1H-NMR spectrum displayed a multiplet at d(H) 1.60 – 1.72,
Fig. 1. 19F-NMR Spectrum of NMR tube reaction (CFCl3 as internal standard)
Fig. 2. 19F-NMR Spectrum of the prepared piperidinium trifluoroacetate (CFCl3 as internal standard)
1
)
Standard piperidinium trifluoroacetate salt was prepared by mixing piperidine and CF3COOH in
CDCl3 at low temperatures.

Helvetica Chimica Acta – Vol. 96 (2013)
1551
corresponding to two H-atoms, another multiplet at d(H) 1.74 – 1.90 corresponding to
four H-atoms, and the H-atoms adjacent to an N-atom due to the deshielding gave rise
to a further multiplet at d(H) 3.12 – 3.22.
Knoevenagel product 5 (15% yield) was prepared as outlined in Scheme 3 [9] by the
condensation of 1g (1 mmol) with 2a (1 mmol), in AcOH and piperidine (1 mmol) and
1
using dry benzene (Scheme 3). Compound 5 was characterized by H-NMR, and an
attempt was carried out with 5 (1 mmol) and piperidine (1.2 mmol) in CH2Cl2 at room
temperature. The progress of the reaction was monitored by TLC, and formation of the
desired product 3ze was not detected (1H-NMR). Even under reflux, the attempt did
1
not give the desired compound 3ze (TLC and H-NMR), and starting material 5 was
recovered. Thus, the present reaction proceeded only through the formation of primary
aldol adduct; further attack of piperidine at trifluoroacetyl C¼O C-atom, followed by in
situ stereoselective elimination of piperidinium trifluoroacetate provided (E)-a,b-
unsaturated ester (Schemes 1 – 3). Having obtained the results with piperidine, next we
have tested various secondary amines such as pyrrolidine, piperazine, 1-methylpiper-
azine, 1-phenylpiperazine, 1-benzylpiperazine, morpholine, iPr2NH, Et2NH, and
Me2NH in the reaction of 1g with 2a in CH2Cl2 at room temperature. Among these,
pyrrolidine was found to be better (40 h, 82% yield) to give 3ze, compared to other
bases (2 – 4 equiv., 60 – 70 h, 15 – 30%). Piperidine in combination of CH2Cl2 turned out
as the better system, and 1 mol of piperidine was essential to form piperidinium
trifluoroacetate to provide (E)-a,b-unsaturated esters and ketones [7].
Scheme 3
Having succeeded in the preparation of (E)-a,b-unsaturated esters with ethyl 4,4,4-
trifluoro-3-oxobutanoate; next ethyl 4,4,4-trichloro-3-oxobutanoate (2b) was tested
with carbonyl compounds to evaluate the feasibility of the reaction. Accordingly, under
optimized conditions 2b was reacted with 1f and 1g, and the products 3zd and 3ze,
respectively, were obtained in low yields (48 h, 58%; Scheme 4), presumably due to the
less powerful withdrawing effect of the CCl3 group compared to CF3 group present in
the 3-oxo ester. These results encouraged us to carry out the reactions of various
aromatic and heteroaromatic carbonyl compounds, 1a and 1b, and 1c – 1j, respectively,
with various oxobutanoates such as 1,1,1,5,5,5-hexafluoropentane-2,4-dione (2c), 4,4,4-
trifluoro-1-(naphthalene-2-yl)butane-1,3-dione (2d), and 4,4,4-trifluoro-1-(furan-2-
Scheme 4

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Helvetica Chimica Acta – Vol. 96 (2013)
yl)butane-1,3-dione (2e) under optimized conditions resulting in formation of series of
new products 3a – 3t in very good yields (cf. Scheme 5 and Table 1). The synthesis of
1,1,1-trifluoro-4-phenylbut-3-en-2-one (3b) was reported in the literature by the
reaction of benzaldehyde with 1,1,1-trifluoropentane-2,4-dione or 1,1,1-trifluoroacet-
one with piperidine/AcOH in benzene [9][10], and by Wittig reagent [11], whereas the
present simple preparation of 3b involves the reaction of benzaldehyde with 1,1,1,5,5,5-
hexafluoropentane-2,4-dione (2c) using piperidine in CH2Cl2 at ambient/reflux
Scheme 5
Table 1. Synthesis of (E)-a,b-Unsaturated Ketonesa)
Entry Com-
pound 1
Ar
Com-
pound 2
R
Prod- Yield
uct 3
[%]b)c)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
1a
Ph
Ph
2c
2d
2e
2e
2e
2c
2c
2d
2e
2c
2d
2e
2c
Furan-2-yl
CF3
Naphthalen-2-yl 3c
Naphthalen-2-yl 3d
Naphthalen-2-yl 3e
Furan-2-yl
Furan-2-yl
CF3
Naphthalen-2-yl 3i
Furan-2-yl
CF3
Naphthalen-2-yl 3l
Furan-2-yl
3a
3b
87
70
88
89
91
85
84
68
83
86
65
84
83
85
1a
1b
1c
1d
1e
1d
1f
1f
1f
1g
1g
1g
1h
4-BrꢀC6H4
Pyridin-2-yl
Pyridin-4-yl
Pyridin-3-yl
Pyridin-4-yl
2-Chloro-5-methylpyridin-3-yl
2-Chloro-5-methylpyridin-3-yl
2-Chloro-5-methylpyridin-3-yl
2-Chloro-5-phenylpyridin-3-yl
2-Chloro-5-phenylpyridin-3-yl
2-Chloro-5-phenylpyridin-3-yl
3f
3g
3h
3j
3k
3m
2-Chloro-5-(4-methoxyphenyl)- 2e
Naphthalen-2-yl 3n
pyridin-3-yl
15
16
17
18
19
20
1i
1i
1i
1j
1j
1j
2-Chloroquinolin-3-yl
2-Chloroquinolin-3-yl
2-Chloroquinolin-3-yl
2-Chloro-8-methylquinolin-3-yl
2-Chloro-8-methylquinolin-3-yl
2-Chloro-8-methylquinolin-3-yl
2e
2c
2d
2e
2c
2d
Naphthalen-2-yl 3o
82
86
67
83
84
64
Furan-2-yl
CF3
3p
3q
Naphthalen-2-yl 3r
Furan-2-yl
CF3
3s
3t
a) Conditions: aldehyde (1 mmol), trifluoro 1,3-diketones (1.2 mmol), piperidine (1.2 mmol). b) Yields
c
of isolated products; not optimized. ) (E)-Isomer (1H-NMR).

Helvetica Chimica Acta – Vol. 96 (2013)
1553
conditions. The preparation of new unsaturated trifluoromethyl ketones such as 3h, 3k,
3t, and 3q has also been achieved by the present method. Substituted cinnamaldehydes
1p and 1q were also tested with 2a and 2f at room temperature/reflux conditions;
however, the desired product could not be obtained.
Further, the method was applied to the synthesis of chiral derivatives 3zo and 3zp,
starting from 1s with 2a and 2g, respectively, in CH2Cl2 at room temperature under
optimized conditions. Compound 3zo is an important chiral synthon utilized for the
synthesis of various natural products (Scheme 6) [12]. Compound 3zq [13] was
successfully prepared by the reaction of 2a with 1t under similar conditions
t
(deprotection of BuPh2Si (TBDPS); Scheme 7).
Scheme 6
Scheme 7
Having succeeded in the synthesis of a series of (E)-a,b-unsaturated esters and
ketones by conventional methods, next we studied the microwave-assisted synthesis of
(E)-a,b-unsaturated esters and ketones under solvent-free conditions. Microwave-
assisted reactions are considered to be superior to conventional reactions due to
substantial rate enhancement for the synthesis of various natural products and
heterocyclic compounds. Moreover, majority of the microwave-assisted reactions
proceed solvent-free; hence, they are considered to be clean, efficient, and economical
[14]. Solvent-free syntheses of (E)-a,b-unsaturated esters and ketones by the reaction
of carbonyl compounds with ethyl 4,4,4-trifluoro-3-oxobutanoate (2a), 4,4,4-trifluoro-
1-(naphthalene-2-yl)butane-1,3-dione (2d), 4,4,4-trifluoro-1-(furan-2-yl)butane-1,3-di-
one 2e), 1,1,1-trifluoropentane-2,4-dione (2f), and 4,4,4,-trifluoro-1-phenylbutane-1,3-
dione (2g) have not been reported so far.
We performed the microwave (MW)-assisted reactions in CEM [15] Discover
microwave apparatus. Aldehyde 1b (1 mmol), 2a (1.2 mmol), and piperidine
(1.2 mmol) were dissolved in Et2O, neutral Al2O3 was added, and the solvent was
removed under reduced pressure below 288. The adsorbed solid was taken up for
irradiation with 100 W. We monitored the progress of the reaction by TLC and found
that the conversion poor in 2 – 9 min (15 – 28%; Table 2, Entries 1 – 4); however, the
conversion was improved to 90% with 150-W irradiation (16 min; Table 2, Entries 5 – 9)
to give ethyl (E)-3-(4-bromophenyl)acrylate (3w).

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Helvetica Chimica Acta – Vol. 96 (2013)
Table 2. Optimization of Microwave-Assisted Reactionsa)
Entry
Time [min]
Power [W]
Yield [%]b)
1
2
3
4
5
6
7
8
9
3
5
7
9
5
100
100
100
100
150
150
150
150
150
150
–
Trace
15
21
28
34
37
59
88
90
7
10
14
16
14
300
10c)
11d)
90
92
a) Conditions: aldehyde (1 mmol), ethyl 4,4,4-trifluoro-3-oxobutanoate (1.2 mmol), piperidine
(1.2 mmol). b) Yields of isolated products; not optimized. c) Piperidine (1.5 mmol). d) CH2Cl2, r.t.
To evaluate the efficiency of this methodology, reactions of various substituted
aromatic (Table 3, Entries 1 – 8), aliphatic (Table 3, Entry 9), and heteroaromatic
(Table 3, Entries 10 – 29) carbonyl compounds with oxobutanoates, such as 2a, 2d, 2e,
2f, and 2g, were studied to give the corresponding (E)-a,b-unsaturated esters and
ketones 3c – 3zn in good yields. Further, the method was extended to the reaction of
cinnamaldehyde (1p) with 2a under optimized conditions. A colorless solid was
obtained, and spectral evaluation indicated that the formed compound was not the
desired (E,E)-unsaturated ester (1H-NMR; Scheme 8). However, reactions of cinna-
maldehydes 1p – 1r with 1,3-diketones 2d, 2f, and 2g afforded the corresponding (E,E)-
unsaturated ketones 3zj – 3zn (Scheme 9, and Table 3, Entries 30 – 34). Thus, the
synthesized compounds were well characterized on the basis of their spectral data; the
data of known compounds 3u, 3w, 3y, 3z, 3za, 3zh, 3zc, 3zd, 3ze [7], 3b [11], 3a, 3c, 3t, 3g,
Scheme 8
Scheme 9

Helvetica Chimica Acta – Vol. 96 (2013)
1555
Table 3. Microwave-Assisted Synthesis of (E)-a,b-Unsaturated Esters and Ketonesa)
Entry
1
Ar
2
R
Prod- Yield
uct 3
[%]b)c)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
1a
1a
1b
1b
1b
1k
1l
Ph
Ph
2a EtO
2f Me
2a EtO
2g Ph
2e Naphthalen-2-yl 3c
2a EtO
2a EtO
3u
3v
3w
3x
90
87
89
87
88
89
88
86
71
90
86
84
85
83
90
83
86
92
84
83
91
85
82
86
83
84
86
82
85
4-BrꢀC6H4
4-BrꢀC6H4
4-BrꢀC6H4
4-MeOꢀC6H4
4-ClꢀC6H4
4-ClꢀC6H4
3y
3z
3za
3zb
3zc
1l
2f
Me
1m Pentyl
2a EtO
2a EtO
2e Naphthalen-2-yl 3d
2e Naphthalen-2-yl 3e
1c
1c
1d
1e
1d
1f
1f
1f
1g
1g
1g
1h
1h
1i
1i
1j
1j
1n
1n
1o
Pyridin-2-yl
Pyridin-2-yl
Pyridin-4-yl
Pyridin-3-yl
2c
2c
Furan-2-yl
Furan-2-yl
3f
3g
3zd
Pyridin-4-yl
2-Chloro-5-methylpyridin-3-yl
2-Chloro-5-methylpyridin-3-yl
2-Chloro-5-methylpyridin-3-yl
2-Chloro-5-phenylpyridin-3-yl
2-Chloro-5-phenylpyridin-3-yl
2-Chloro-5-phenylpyridin-3-yl
2-Chloro-5-(4-methoxyphenyl)pyridin-3-yl 2g Ph
2-Chloro-5-(4-methoxyphenyl)pyridin-3-yl 2e Naphthalen-2-yl 3n
2-Chloroquinolin-3-yl
2-Chloroquinolin-3-yl
2-Chloro-8-methylquinolin-3-yl
2-Chloro-8-methylquinolin-3-yl
6-Bromo-1,3-benzodioxol-5-yl
6-Bromo-1,3-benzodioxol-5-yl
5-Bromo-1-[(tert-butoxy)carbonyl]-
1H-indole-3-yl
2a EtO
2e Naphthalen-2-yl 3i
2c
Furan-2-yl
3j
3ze
2a EtO
2e Naphthalen-2-yl 3l
2c
Furan-2-yl
3m
3zf
2e Naphthalen-2-yl 3o
2c Furan-2-yl 3p
2e Naphthalen-2-yl 3r
2c
Furan-2-yl
3s
3zg
2g Ph
2e Naphthalen-2-yl 3zh
2e Naphthalen-2-yl 3zi
30
31
32
33
34
1p
1p
1p
1q
1r
PhꢀCH¼CH (E)
2f
2g Ph
2e Naphthalen-2-yl 3zl
2g Ph
2g Ph
Me
3zj
3zk
60
63
58
48
51
PhꢀCH¼CH (E)
PhꢀCH¼CH (E)
4-NO2ꢀC6H4ꢀCH¼CH (E)
3zm
3zn
2-MeOꢀC6H4ꢀCH¼CH (E)
a) Conditions: aldehyde (1 mmol), trifluoro 1,3-diketo ester/ketone (1.2 mmol), piperidine (1.2 mmol),
Microwave irradiation (150 W). b) Yields of isolated products; not optimized. c) (E)-isomer
(1H-NMR).
3v, 3zj, 3x, 3zk, 3zl, 3zm, 3zn [16], 3zo, 3zp [12], and 3zq [13] were compared with those
in the literature. New compounds 3d, 3e, 3h – 3t, and 3zf – 3zi were identified by means
1
of their H- and 13C-NMR, MS, IR, and ESI-HR-MS data (see Exper. Part).

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Helvetica Chimica Acta – Vol. 96 (2013)
Conclusions. – In conclusion, an efficient method has been established for the
synthesis of (E)-a,b-unsaturated esters and ketones by the reaction of carbonyl
compounds with trifluoro-oxobutanoates/1,3-diketones. The reactions proceed through
the formation of aldol primary adduct and in situ stereoselective elimination of
piperidinium trifluoroacetate. The method also opens a new way for C,C bond
formations.
The authors thank Dr. J. S. Yadav, Director, and Dr. S. Chandrasekhar, Head, Natural Products
Chemistry Division, CSIR-IICT, for their constant encouragement and support of this work. The authors
thank Dr. T. Prabhakar Rao, NMR division, CSIR-IICT, for providing the spectral data. Financial
assistance to P. S. and R. N. R. from CSIR, New Delhi, is gratefully acknowledged.
Experimental Part
General. The chemicals, trifluoro 1,3-diketones/b-keto esters (Aldrich), piperidine, and all the
solvents were obtained from local suppliers. Column chromatography (CC): silica gel (SiO2; 60 –
120 mesh). M.p.: Mettler-Temp apparatus; uncorrected. IR Spectra: Perkin-Elmer-1600 FT-IR spec-
1
trometer; in KBr; ˜n in cmꢀ1. H- and 13C-NMR spectra: Bruker-Avance-300 spectrometer; in CDCl3;
chemical shifts, d, in ppm rel. to Me4Si as internal standard; J in Hz. ESI-MS: 7070 H spectrometer with a
direct inlet system; in m/z (rel. %). ESI-HR-MS: Agilent 6510 Q-TOF LC/MS instrument. Microwave
(MW) irradiation: CEMTM Discovery instrument.
Representative Procedure for the Synthesis of (E)-a,b-Unsaturated Esters/Ketones. Piperidine
(1.2 mmol) was added to a stirred soln. of 2-chloro-5-methylnicotinaldehyde (1f; 1.0 mmol) and ethyl
4,4,4-trifluoro-3-oxobutanoate/4,4,4-trifluoro-1-(naphthalene-2-yl)butane-1,3-dione (2a/2d; 1.2 mmol) in
CH2Cl2 (2 ml), and the mixture was refluxed for 2 to 3 h (TLC). After completion of reaction, the
mixture was further diluted with CH2Cl2, and the contents were washed with H2O, the org. layer was
separated, dried (Na2SO4), and the solvent was removed under reduced pressure. The residue was
purified by CC (hexane/AcOEt 9 :1) to afford the 3zd/3i as a colorless solid/solid in 90/83% yield.
Representative Procedure for MW-Assisted Synthesis of (E)-a,b-Unsaturated Esters and Ketones. A
mixture of 4-bromobenzaldehyde (1b; 1.0 mmol), ethyl 4,4,4-trifluoro-3-oxobutanoate (2a; 1.2 mmol),
and piperidine (1.2 mmol) was added to neutral Al2O3 (200 mg) in Et2O (2 ml). The solvent was
evaporated under reduced pressure at moderate temp. (288), and then the mixture was poured into a
capped 10-ml microwave vessel. The mixture was irradiated for 16 min with 150 W, monitored by TLC;
after completion of the reaction, the residue was purified by flash CC to give 3w (89%) as a colorless
liquid.
(2E)-1-(Naphthalen-2-yl)-3-(pyridin-2-yl)prop-2-en-1-one (3d). Yield: 86%. Yellow solid. M.p. 80 –
828. IR: 2925, 2853, 1661, 1608, 1467, 776. 1H-NMR: 7.24 – 7.30 (m, 1 H); 7.44 (d, J ¼ 7.6, 1 H); 7.48 – 7.60
(m, 2 H); 7.60 – 7.92 (m, 4 H); 7.98 (d, J ¼ 8.3, 1 H); 8.12 – 8.18 (m, 1 H); 8.30 (d, J ¼ 15.1, 1 olef. H); 8.62
(s, 1 H); 8.68 (d, J ¼ 4.5, 1 H). 13C-NMR: 124.2; 124.5; 125.5; 126.7; 127.8; 128.4; 128.5; 129.6; 130.4;
132.6; 135.2; 135.6; 136.7; 142.3; 150.1; 153.3; 189.5. ESI-MS: 260 ([M þ H]þ). ESI-HR-MS: 260.107
([M þ H]þ, C18H14NOþ; calc. 260.1075).
(2E)-1-(Naphthalen-2-yl)-3-(pyridin-4-yl)prop-2-en-1-one (3e). Yield: 84%. Brown solid. M.p. 84 –
868. IR: 2923, 1662, 1462, 809, 757. 1H-NMR: 7.48 – 7.78 (m, 5 H); 7.82 (d, J ¼ 15.9, 1 olef. H); 7.86 – 8.10
(m, 4 H); 8.50 (s, 1 H); 8.70 (d, J ¼ 4.7, 2 H). 13C-NMR: 122.1; 124.4; 126.0; 127.0; 127.9; 128.7; 128.8;
129.6; 130.2; 135.0; 135.7; 135.9; 141.3; 142.3; 150.5; 188.8. ESI-MS: 260 ([M þ H]þ). ESI-HR-MS:
260.107 ([M þ H]þ, C18H14NOþ; calc. 260.1075).
(3E)-4-(2-Chloro-5-methylpyridin-3-yl)-1,1,1-trifluorobut-3-en-2-one (3h). Yield: 68%. Colorless
solid. M.p. 148 – 1508. IR: 2921, 2851, 1718, 1608, 1145, 980, 869. 1H-NMR: 2.42 (s, Me); 6.98 (d, J ¼ 16.2, 1
olef. H); 7.81 (s, 1 H); 8.25 (d, J ¼ 16.2, 1 olef. H); 8.29 (s, 1 H). 13C-NMR: 29.7; 120.2; 127.6; 132.7; 132.8;
136.5; 144.1; 149.9; 152.35; 186.4. 19F-NMR: ꢀ 78.16.

Helvetica Chimica Acta – Vol. 96 (2013)
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(2E)-3-(2-Chloro-5-methylpyridin-3-yl)-1-(naphthalen-2-yl)prop-2-en-1-one (3i). Yield: 83%. Pale-
yellow solid. M.p. 112 – 1148. IR: 2921, 1660, 1604, 1464, 1170. 1H-NMR: 2.42 (s, Me); 7.52 – 7.62 (m, 3 H);
7.84 – 8.08 (m, 6 H); 8.22 (d, J ¼ 2.1, 1 H); 8.48 (s, 1 H). 13C-NMR: 17.7; 124.4; 126.0; 126.7; 127.6; 128.4;
128.6; 129.3; 129.5; 130.0; 132.3; 132.5; 134.9; 135.5; 136.3; 138.7; 149.1; 150.6; 188.4. ESI-MS: 308/310
([M þ H]þ). ESI-HR-MS: 308.0863 ([M þ H]þ, C19H15ClNOþ; calc. 308.0842).
(2E)-3-(2-Chloro-5-methylpyridin-3-yl)-1-(furan-2-yl)prop-2-en-1-one (3j). Yield: 86%. Colorless
solid. M.p. 95 – 978. 1H-NMR: 2.40 (s, Me); 6.60 (dd, J ¼ 1.7, 3.6, 1 H); 7.32 (dd, J ¼ 1.0, 2.9, 1 H); 7.41 (d,
J ¼ 15.9, 1 olef. H); 7.64 (s, 1 H); 7.82 (s, 1 H); 8.08 (d, J ¼ 15.9, 1 olef. H); 8.21 (s, 1 H). 13C-NMR: 17.6;
112.7; 118.1; 125.2; 128.9; 132.7; 136.5; 138.1; 146.8; 149.0; 150.9; 153.2; 177.0. ESI-MS: 248/250 ([M þ
H]þ). ESI-HR-MS: 248.0472 ([M þ H]þ, C13H11ClNOþ2 ; calc. 248.0478).
(3E)-4-(2-Chloro-5-phenylpyridin-3-yl)-1,1,1-trifluorobut-3-en-2-one (3k). Yield: 65%. Colorless
1
solid. M.p. 162 – 1648. H-NMR: 7.06 (d, J ¼ 15.5, 1 olef. H); 7.40 – 7.58 (m, 5 H); 8.12 (d, J ¼ 2.5, 1 H);
8.31 (d, J ¼ 16.1, 1 olef. H); 8.66 (d, J ¼ 2.3, 1 H). 13C-NMR: 120.8; 127.1; 128.1; 129.1; 129.4; 129.5; 129.5;
134.6; 135.5; 136.7; 144.2; 150.3; 178.6.
(2E)-3-(2-Chloro-5-phenylpyridin-3-yl)-1-(naphthalen-2-yl)prop-2-en-1-one (3l). Yield: 84%. Pale-
yellow solid. M.p. 106 – 1088. IR: 2920, 1645, 1610, 1465. 1H-NMR: 7.36 – 7.62 (m, 7 H); 7.68 (d, J ¼ 15.9, 1
olef. H); 7.84 – 8.20 (m, 6 H); 8.50 (s, 1 H); 8.58 (d, J ¼ 2.3, 1 H). 13C-NMR: 124.0; 124.5; 126.6; 126.8;
127.2; 127.9; 128.5; 128.7; 129.0; 129.3; 129.5; 130.2; 131.0; 132.5; 134.2; 135.5; 136.2; 138.1; 138.8; 147.3;
148.5; 188.5. ESI-MS: 370/372 ([M þ H]þ). ESI-HR-MS: 370.1004 ([M þ H]þ, C24H17ClNOþ; calc.
370.0999).
(2E)-3-(2-Chloro-5-phenylpyridin-3-yl)-1-(furan-2-yl)prop-2-en-1-one (3m). Yield: 83%. Colorless
solid. M.p. 116 – 1188. 1H-NMR: 6.60 (dd, J ¼ 1.5, 3.8, 1 H); 7.36 (d, J ¼ 3.8, 1 H); 7.42 – 7.58 (m, 6 H); 7.62
(d, J ¼ 15.1, 1 olef. H); 8.14 (d, J ¼ 3.0, 1 H); 8.18 (d, J ¼ 2.3, 1 H); 8.58 (d, J ¼ 3.0, 1 H). 13C-NMR: 112.8;
117.8; 125.6; 127.1; 128.7; 129.3; 129.6; 134.2; 136.1; 136.3; 138.1; 146.4; 148.7; 150.7; 153.5; 176.6. ESI-MS:
310/312 ([M þ H]þ). ESI-HR-MS: 310.064 ([M þ H]þ, C18H13ClNOþ2 ; calc. 310.0635).
(2E)-3-[2-Chloro-5-(4-methoxyphenyl)pyridin-3-yl]-1-(naphthalen-2-yl)prop-2-en-1-one (3n).
Yield: 85%. Pale yellow solid. M.p. 112 – 1148. IR: 2926, 1640, 1608, 1460, 1031. 1H-NMR: 3.88 (s,
MeO); 7.00 (d, J ¼ 9.1, 2 H); 7.50 – 7.62 (m, 4 H); 7.66 (d, J ¼ 15.9, 1 olef. H); 7.86 – 8.16 (m, 6 H); 8.50 (s,
1 H); 8.56 (d, J ¼ 2.3, 1 H). 13C-NMR: 55.4; 114.5; 114.8; 124.4; 126.7; 127.9; 128.3; 128.7; 128.8; 129.5;
130.4; 131.2; 132.4; 133.9; 134.8; 135.2; 135.6; 136.0; 137.5; 139.1; 148.4; 189.6. ESI-MS: 400 ([M þ H]þ).
ESI-HR-MS: 400.110 ([M þ H]þ, C25H19ClNO2þ ; calc. 400.1104).
(2E)-3-(2-Chloroquinolin-3-yl)-1-(naphthalen-2-yl)prop-2-en-1-one (3o). Yield: 82%. Pale yellow
solid. M.p. 182 – 1848. IR: 2924, 1662, 1465, 762. 1H-NMR: 7.54 – 7.63 (m, 3 H); 7.72 (d, J ¼ 15.7, 1 olef. H);
7.76 (t, J ¼ 6.8, 1 H); 7.86 – 8.14 (m, 6 H); 8.24 (d, J ¼ 15.7, 1 olef. H); 8.50 (s, 1 H); 8.54 (s, 1 H).
13C-NMR: 123.7; 124.5; 126.4; 126.8; 127.0; 127.1; 127.8; 127.9; 123.1; 128.7; 128.8; 129.4; 129.6; 130.5;
131.7; 136.3; 139.4; 148.0; 189.7. ESI-MS: 344/346 ([M þ H]þ). ESI-HR-MS: 344.0833 ([M þ H]þ,
C22H15ClNOþ; calc. 344.0842).
(2E)-3-(2-Chloroquinolin-3-yl)-1-(furan-2-yl)prop-2-en-1-one (3p). Yield: 86%. Pale-yellow solid.
M.p. 168 – 1708. 1H-NMR: 6.62 (dd, J ¼ 2.3, 3.8, 1 H); 7.36 (d, J ¼ 3.0, 1 H); 7.54 (d, J ¼ 7.6, 1 H); 7.58 (d,
J ¼ 8.3, 1 H); 7.64 (d, J ¼ 15.1, 1 olef. H); 7.72 – 7.80 (m, 1 H); 7.86 (d, J ¼ 8.3, 1 H); 8.02 (d, J ¼ 9.1, 1 H);
8.26 (d, J ¼ 15.9, 1 olef. H); 8.47 (s, 1 H). 13C-NMR: 12.9; 118.3; 125.4; 127.0; 127.3; 127.7; 128.1; 128.5;
131.7; 136.0; 136.3; 138.5; 146.3; 146.9; 147.9; 186.2. ESI-MS: 284/286 ([M þ H]þ). ESI-HR-MS: 284.048
([M þ H]þ, C16H11ClNOþ2 ; calc. 284.0478).
(3E)-4-(2-Chloroquinolin-3-yl)-1,1,1-trifluorobut-3-en-2-one (3q). Yield: 67%. Pale-brown solid.
M.p. 132 – 1348. 1H-NMR: 7.12 (d, J ¼ 15.86, 1 olef. H); 7.62 (t, J ¼ 6.8, 1 H); 7.78 – 7.90 (m, 2 H); 8.02 (d,
J ¼ 8.3, 1 H); 8.42 (d, J ¼ 15.9, 1 olef. H); 8.48 (s, 1 H). 13C-NMR: 120.3; 128.1; 128.4; 128.6; 132.6; 137.2;
137.6; 143.7; 144.6; 144.9; 148.6; 150.3; 182.0.
(2E)-3-(2-Chloro-8-methylquinolin-3-yl)-1-(naphthalen-2-yl)prop-2-en-1-one (3r). Yield: 83%.
1
Pale-yellow solid. M.p. 178 – 1808. IR: 2923, 1660, 1597, 1468, 1171, 743. H-NMR: 2.78 (s, Me); 7.42 –
7.74 (m, 6 H); 7.82 – 8.00 (m, 3 H); 8.10 (d, J ¼ 8.5, 1 H); 8.24 (d, J ¼ 15.7, 1 olef. H); 8.44 (s, 1 H); 8.52
(s, 1 H). 13C-NMR: 29.7; 124.0; 124.6; 125.7; 125.9; 126.7; 127.2; 127.8; 128.4; 128.6; 129.5; 130.1; 131.4;
132.6; 135.1; 135.3; 135.6; 136.1; 137.0; 139.5; 147.2; 149.4; 188.5. ESI-MS: 358/360 ([M þ H]þ). ESI-HR-
MS: 358.167 ([M þ H]þ, C23H17ClNOþ; calc. 358.0999).

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Helvetica Chimica Acta – Vol. 96 (2013)
(2E)-3-(2-Chloro-8-methylquinolin-3-yl)-1-(furan-2-yl)prop-2-en-1-one (3s). Yield: 84%. Pale-yel-
low solid. M.p. 164 – 1668. 1H-NMR: 2.76 (s, Me); 6.62 (dd, J ¼ 1.5, 3.0, 1 H); 7.36 (d, J ¼ 3.8, 1 H); 7.46 (t,
J ¼ 8.3, 1 H); 7.54 (d, J ¼ 15.9, 1 olef. H); 7.58 (d, J ¼ 7.6, 1 H); 7.65 – 7.70 (m, 2 H); 8.28 (d, J ¼ 15.9, 1 olef.
H), 8.44 (s, 1 H). 13C-NMR: 41.1; 112.8; 118.2; 125.3; 127.0; 127.2; 127.7; 128.0; 128.4; 131.6; 135.9; 136.2;
138.4; 146.9; 151.0; 151.9; 186.1. ESI-MS: 298/300 ([M þ H]þ).
(3E)-4-(2-Chloro-8-methylquinolin-3-yl)-1,1,1-trifluorobut-3-en-2-one (3t). Yield: 64%. Pale-brown
1
solid. M.p. 128 – 1308. H-NMR: 2.78 (s, Me); 7.12 (d, J ¼ 15.9, 1 olef. H); 7.46 (d, J ¼ 15.1, 1 olef. H);
7.62 – 7.72 (m, 2 H); 8.40 (s, 1 H); 8.45 (s, 1 H). 13C-NMR: 29.7; 119.9; 125.8; 126.3; 126.8; 127.9; 132.2;
132.7; 137.0; 137.4; 144.9; 147.8; 149.2; 179.7.
(2E)-3-[2-Chloro-5-(4-methoxyphenyl)pyridin-3-yl]-1-phenylprop-2-en-1-one (3zf). Yield: 91%.
Colorless solid. M.p. 125 – 1278. IR: 2924, 1641, 1604, 1458, 1028. 1H-NMR: 3.86 (s, MeO); 6.98 (d, J ¼
15.1, 1 olef. H); 7.00 (d, J ¼ 9.1, 1 H); 7.46 – 7.52 (m, 3 H); 7.54 (d, J ¼ 15.9, 1 olef. H); 7.56 – 7.62 (m,
2 H); 7.99 (d, J ¼ 8.3, 1 H); 8.03 (d, J ¼ 6.8, 2 H); 8.08 (s, 1 H); 8.55 (d, J ¼ 2.3, 1 H). 13C-NMR: 55.3;
114.9; 126.6; 128.3; 128.7; 128.8; 129.8; 133.0; 133.8; 135.3; 136.0; 137.7; 139.2; 147.0; 148.3; 160.4; 188.9.
ESI-MS: 350/352 ([M þ H]þ). ESI-HR-MS: 350.0956 ([M þ H]þ, C21H17ClNOþ2 ; calc. 350.0948).
(2E)-3-(6-Bromo-1,3-benzodioxol-5-yl)-1-phenylprop-2-en-1-one (3zg). Yield: 86%. Colorless solid.
M.p. 140 – 1428. 1H-NMR: 6.04 (s, 2 H); 7.06 (s, 1 H); 7.20 (s, 1 H); 7.28 (d, J ¼ 15.9, 1 olef. H); 7.44 – 7.59
(m, 3 H); 7.94 – 5.02 (m, 2 H); 8.04 (d, J ¼ 15.1, 1 olef. H). 13C-NMR: 102.2; 106.5; 113.4; 118.8; 123.0;
126.8; 128.4; 128.6; 132.7; 138.2; 143.0; 147.9; 150.2; 189.6. ESI-MS: 331/333 ([M þ H]þ).
(2E)-3-(6-Bromo-1,3-benzodioxol-5-yl)-1-(naphthalen-2-yl)prop-2-en-1-one (3zh). Yield: 82%. Yel-
low solid. M.p. 146 – 1488. 1H-NMR: 6.06 (s, 2 H); 7.08 (s, 1 H); 7.24 (s, 1 H); 7.40 (d, J ¼ 15.1, 1 olef. H);
7.48 – 7.62 (m, 2 H); 7.84 – 7.98 (m, 3 H); 8.05 (d, J ¼ 8.1, 1 olef. H); 8.12 (d, J ¼ 15.9, 1 olef. H); 8.48 (s,
1 H). 13C-NMR: 102.3; 106.5; 113.3; 118.8; 123.0; 124.5; 126.8; 127.8; 128.3; 128.4; 128.6; 129.5; 130.0;
132.5; 135.4; 135.5; 143.1; 148.0; 150.2; 190.1. ESI-MS: 381/383 ([M þ H]þ).
tert-Butyl 5-Bromo-3-[(1E)-3-(naphthalen-2-yl)-3-oxoprop-1-en-1-yl]-1H-indole-1-carboxylate
1
t
(3zi). Yield: 85%. Pale yellow solid. M.p. 130 – 1328. H-NMR: 1.70 (s, Bu); 7.46 – 7.62 (m, 3 H); 7.68
(d, J ¼ 15.9, 1 olef. H); 7.88 (d, J ¼ 15.9, 1 olef. H); 7.90 – 8.02 (m, 4 H); 8.06 (d, J ¼ 1.9, 1 H); 8.10 (d, J ¼
8.7, 2 H), 8.51 (s, 1 H). 13C-NMR: 28.3; 29.8; 116.9; 117.2; 117.4; 118.5; 121.9; 123.2; 124.7; 126.7; 127.9;
128.3; 128.3; 128.6; 129.6; 129.7; 129.8; 132.7; 135.1; 135.6; 135.7; 136.1; 161.8; 182.3. ESI-MS: 476/478
([M þ H]þ). ESI-HR-MS: 476.0856 ([M þ H]þ, C26H23BrNOþ3 ; calc. 476.0861).
Synthesis of Ethyl (2E)-2-[(2-Chloro-5-phenylpyridin-3-yl)methylidene]-4,4,4-trifluoro-3-oxobutan-
oate (5). 2-Chloro-5-phenylnicotinaldehyde (1g; 1 mmol) and ethyl 4,4,4-trifluoro-3-oxobutanoate (2a,
1 mmol) were dissolved in dry benzene (10 ml). Piperidine (0.2 ml) and AcOEt (0.3 ml) were added, and
the mixture was refluxed using DeanꢀStark azeotropic distillation apparatus for 16 – 20 h. H2O was
added, the phases were separated, and the org. layer was washed with dil. HCl, followed by H2O, org.
layer was dried (MgSO4), and the solvent was removed under reduced pressure. The obtained oil was
purified by CC (SiO2; hexane/AcOEt). 1H-NMR: 1.44 (t, J ¼ 7.2, Me); 4.46 (q, J ¼ 7.2, 2 H, CH2O); 7.44 –
7.64 (m, 5 H); 8.64 (s, 1 H); 8.70 (d, J ¼ 1.7, 1 H); 8.76 (d, J ¼ 1.7, 1 H).
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Received September 14, 2012