An environmentally benign catalytic method for versatile synthesis of 1,4-dihydropyridines via multicomponent reactions

Article abstract of DOI:10.1002/cjoc.201500195

The synthesis of diverse 1,4-dihydropyridines have been achieved via the multicomponent reactions of aldehydes, enaminones and amines. The reactions have been smoothly performed in water to provide all products with moderate to excellent yields by using l

Full text of DOI:10.1002/cjoc.201500195

FULL PAPER
DOI: 10.1002/cjoc.201500195
An Environmentally Benign Catalytic Method for Versatile
Synthesis of 1,4-Dihydropyridines via Multicomponent
Reactions
Shuo Cao,a Shanshan Zhong,a Changfeng Hu,b Jie-Ping Wan,*,a and Chengping Wen*,b
a Key Laboratory of Functional Small Organic Molecule, Ministry of Education, College of Chemistry and
Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022, China
b College of Basic Medical Sciences, Zhejiang Chinese Medical University, Hangzhou, Zhejiang 310053, China
The synthesis of diverse 1,4-dihydropyridines have been achieved via the multicomponent reactions of alde-
hydes, enaminones and amines. The reactions have been smoothly performed in water to provide all products with
moderate to excellent yields by using lactic acid as a green catalyst.
Keywords lactic acid catalysis, multicomponent reactions, 1,4-dihydropyridines, green catalysis, heterocycle
Introduction
Lactic acid (LA) is a low cost natural chemical which
can be easily acquired from bio-mass. As a bio-based
organic product, LA has been broadly employed in
chemical industry as the source of many important
chemical products. The internal features of non-toxicity
as well as versatile reaction and catalytic activity of LA
have attracted tremendous attention in chemical com-
munity.[7] Following our longstanding interests in the
field of multicomponent reactions[8] and environmen-
tally benign synthesis,[7b,9] we report herein the first
LA-catalyzed multicomponent[10] synthesis of diverse
1,4-DHPs by the assemblies of aldehydes, amines,
enaminones in water.
1,4-Dihydropyridines (1,4-DHPs) are well known
heterocyclic scaffolds possessing a broad array of bio-
logical functions.[1] Many 1,4-DHP-based compounds
such as Felodipine, Nicardipine, Nifedipine etc. have
been frequently used in the treatment of hypertension.
Besides the valuable pharmaceutical profiles, 1,4-DHPs
have also been known as useful building blocks in the
synthesis of structurally attractive organic products such
as fused polycyclic molecules.[2] Because of their versa-
tile utilities in organic synthesis, chemical biology and
pharmaceutical chemistry, the 1,4-DHP backbone is
now recognized as a privileged heterocyclic identity,
which results in the everlasting interests in the research
area of 1,4-DHPs synthesis.[3] As the convenient and
classical protocol, the Hantzsch reaction which involves
in the acid promoted assembly of aldehyde, α-ketoester
and ammonium has served significantly in the synthesis
of 1,4-DHPs. However, due to the limit of Hantzsch
reaction in providing 1,4-DHPs of only symmetrical
structure, alternative synthetic protocols that are able to
afford structurally diverse 1,4-DHPs, especially those
containing unsymmetrical structures have emerged as a
new trend in the chemistry of 1,4-DHPs.[4]
Experimental
General procedure for the synthesis of 1,4-DHPs 4
and 6
To a 50 mL tube equiped with a stirring bar were
added aldehyde 2 (0.3 mmol), enaminone 1 or 5 (0.5
mmol), primary amine 3 (0.3 mmol, in the synthesis of
1,4-DHPs 4 only), LA (0.125 mmol) and H2O (2 mL).
The vessel was then sealed with a screw cap and stirred
at 110 ℃ for 20 h. After completion of the reaction
(TLC), the mixture was extracted with ethyl acetate (10
mL×3). The combined organic phase was dried over
anhydrous Na2SO4. After fitration, the solvent was re-
moved from the solution under reduced pressure, the
residue was then subjected to preparative TLC to give
pure product by using mixed ethyl acetate and petro-
leum ether as eluent (VEA∶VPE＝1∶4).
On the other hand, in order to address the issue of
chemistry-based environmental impact, devising sus-
tainable organic synthesis has become one of the main
challenges in the field of organic synthesis. During the
past decade, numerous attentions have been directed to
green organic synthesis by designing reaction using
green media[5] and/or other sustainable techonologies.[6]
(4-(4-Chlorophenyl)-1-(p-tolyl)-1,4-dihydropyridine-
*
E-mail: wanjieping@jxnu.edu.cn; cpwen.zcmu@yahoo.com
Received March 10, 2015; accepted April 9, 2015; published online May 5, 2015.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201500195 or from the author.
568
© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2015, 33, 568—572

Versatile Synthesis of 1,4-Dihydropyridines via Multicomponent Reactions
3,5-diyl)bis(phenylmethanone) (4a):[3h] 1H NMR (400
MHz, CDCl3) δ: 7.53 (d, J＝7.2 Hz, 4H), 7.52－7.43 (m,
3H), 7.38 (t, J＝7.2 Hz, 5H), 7.26 (s, 3H), 7.24 (s, 1H),
7.19 (d, J＝7.6 Hz, 2H), 7.04 (d, J＝8.0 Hz, 2H), 5.66
(s, 1H), 2.34 (s, 3H).
(4-(2-Chlorophenyl)-1-phenyl-1,4-dihydropyridine-
3,5-diyl)bis(phenylmethanone) (4b):[3h] 1H NMR (400
MHz, CDCl3) δ: 7.67 (d, J＝9.2 Hz, 1H), 7.59 (d, J＝
6.8 Hz, 4H), 7.43 (d, J＝7.2 Hz, 2H), 7.39－7.36 (m,
6H), 7.32－7.24 (m, 4H), 7.20－7.14 (m, 3H), 7.07 (td,
J＝7.6, 1.2 Hz, 1H), 6.01 (s, 1H).
(4-(4-Chlorophenyl)-1-phenyl-1,4-dihydropyridine-
3,5-diyl)bis(phenylmethanone) (4c):[3h] 1H NMR (400
MHz, CDCl3) δ: 7.54 (d, J＝7.2 Hz, 4H), 7.46－7.37 (m,
10H), 7.30－7.24 (m, 5H), 7.14 (d, J＝7.6 Hz, 2H),
5.66 (s, 1H).
(4-Phenyl-1-(p-tolyl)-1,4-dihydropyridine-3,5-diyl)-
bis(phenylmethanone) (4d):[3h] 1H NMR (400 MHz,
CDCl3) δ: 7.53 (d, J＝7.6 Hz, 4H), 7.48 (d, J＝8.0 Hz,
2H), 7.43 (d, J＝7.6 Hz, 2H), 7.38 (d, J＝7.2 Hz, 4H),
7.30－7.25 (m, 4H), 7.19 (d, J＝8.4 Hz, 3H), 7.04 (d,
J＝8.0 Hz, 2H), 5.69 (s, 1H), 2.33 (s, 3H).
(4-(4-Chlorophenyl)-1-(p-tolyl)-1,4-dihydropyridine-
3,5-diyl)bis(p-tolylmethanone) (4e):[3h] 1H NMR (400
MHz, CDCl3) δ: 7.44 (t, J＝8.8 Hz, 6H), 7.26 (s, 3H),
7.24－7.17 (m, 7H), 7.04 (d, J＝8.0 Hz, 2H), 5.64 (s,
1H), 2.36 (s, 6H), 2.34 (s, 3H).
(4-(4-Chlorophenyl)-1-phenyl-1,4-dihydropyridine-
3,5-diyl)bis(p-tolylmethanone) (4f):[3h] 1H NMR (400
MHz, CDCl3) δ: 7.47－7.39 (m, 7H), 7.31 (s, 2H), 7.26
(t, J＝6.4 Hz, 3H), 7.22－7.14 (m, 7H), 5.65 (s, 1H),
2.37 (s, 6H).
(4-Phenyl-1-(p-tolyl)-1,4-dihydropyridine-3,5-diyl)-
bis((4-methoxyphenyl)methanone) (4g):[3h] 1H NMR
(400 MHz, CDCl3) δ: 7.56 (d, J＝8.4 Hz, 4H), 7.46 (d,
J＝7.2 Hz, 2H), 7.26－7.24 (m, 4H), 7.19 (d, J＝8.4 Hz,
2H), 7.12 (t, J＝7.2 Hz, 1H), 7.06 (d, J＝8.4 Hz, 2H),
6.87 (d, J＝8.8 Hz, 4H), 5.69 (s, 1H), 3.82 (s, 6H), 2.34
(s, 3H).
(1,4-Diphenyl-1,4-dihydropyridine-3,5-diyl)bis((4-
fluorophenyl)methanone) (4h):[3h] 1H NMR (400 MHz,
CDCl3) δ: 7.58－7.55 (m, 4H), 7.41 (t, J＝8.0 Hz, 4H),
7.32 (d, J＝6.4 Hz, 1H), 7.25 (d, J＝7.6 Hz, 4H), 7.15
(d, J＝7.6 Hz, 3H), 7.08 (t, J＝8.0 Hz, 4H), 5.63 (s,
1H).
120.9, 120.1, 113.7, 55.4, 37.3; ESI-HRMS calcd for
C33H26ClNO4Na [M＋Na]＋ 558.1443, found 558.1435.
(1,4-Bis(4-methoxyphenyl)-1,4-dihydropyridine-3,5-
diyl)bis(phenylmethanone) (4k):[3h] 1H NMR (400 MHz,
CDCl3) δ: 7.53 (d, J＝8.0 Hz, 4H), 7.46－7.35 (m, 8H),
7.17 (s, 2H), 7.09 (d, J＝8.8 Hz, 2H), 6.89 (d, J＝9.2
Hz, 2H), 6.82 (d, J＝8.8 Hz, 2H), 5.62 (s, 1H), 3.78 (s,
3 H), 3.74 (s, 3H).
(1-(4-Chlorophenyl)-4-(p-tolyl)-1,4-dihydropyridine-
3,5-diyl)bis(phenylmethanone) (4l): Yellow solid; m.p.
225－228 ℃; 1H NMR (400 MHz, CDCl3) δ: 7.54 (d,
J＝7.2 Hz, 4H), 7.46 (t, J＝6.8 Hz, 2H), 7.40－7.34 (m,
8H), 7.21 (s, 2H), 7.08 (d, J＝8.4 Hz, 4H), 5.64 (s, 1H),
2.26 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ: 194.5,
142.3, 141.7, 139.0, 138.2, 136.2, 132.3, 131.2, 130.2,
129.2, 128.5, 128.3, 128.1, 122.3, 121.2, 36.6, 21.1;
EI-HRMS calcd for C32H24ClNO2 [M] ＋ 489.1496,
found 489.1500.
(1-(3-Chlorophenyl)-4-(4-methoxyphenyl)-1,4-dihy-
dropyridine-3,5-diyl)bis(phenylmethanone) (4m): Yel-
1
low solid; m.p. 216－219 ℃; H NMR (400 MHz,
CDCl3) δ: 7.55 (d, J＝7.6 Hz, 4H), 7.48 (t, J＝6.8 Hz,
2H), 7.42－7.34 (m, 7H), 7.31 (d, J＝8.0 Hz, 1H), 7.22
(s, 2H), 7.14 (s, 1H), 7.03 (d, J＝8.0 Hz, 1H), 6.81 (d,
J＝8.0 Hz, 2H), 5.61 (s, 1H), 3.74 (s, 3H); 13C NMR
(CDCl3, 100 MHz) δ: 194.6, 158.3, 144.2, 138.9, 137.8,
137.6, 135.8, 131.3, 131.1, 129.2, 128.5, 128.4, 126.8,
121.4, 121.3, 119.1, 113.9, 55.2, 36.3; ESI-HMRS calcd
for C32H24ClNO3 [M]＋ 505.1445, found 505.1441.
3,3,6,6-Tetramethyl-9,10-diphenyl-3,4,6,7,9,10-
hexahydroacridine-1,8(2H,5H)-dione (6a):[11a] 1H NMR
(400 MHz, CDCl3) δ: 7.57 (d, J＝7.2 Hz, 3H), 7.44 (d,
J＝7.6 Hz, 2H), 7.27－7.22 (m, 4H), 7.10 (t, J＝7.2 Hz,
1H), 5.29 (s, 1H), 2.22－2.06 (m, 6H), 1.82 (d, J＝17.2
Hz, 2H), 0.94 (s, 6H), 0.80 (s, 6H).
3,3,6,6-Tetramethyl-10-phenyl-9-(p-tolyl)-3,4,6,7,9,10-
hexahydroacridine-1,8(2H,5H)-dione (6b):[11b] 1H NMR
(400 MHz, CDCl3) δ: 7.56 (d, J＝7.2 Hz, 3H), 7.33 (d,
J＝7.6 Hz, 2H), 7.25 (d, J＝6.8 Hz, 2H), 7.05 (d, J＝
8.0 Hz, 2H), 5.25 (s, 1H), 2.25 (s, 3H), 2.17－2.06 (m,
6H), 1.82 (d, J＝17.2 Hz, 2H), 0.93 (s, 6H), 0.80 (s,
6H).
9-(4-Bromophenyl)-3,3,6,6-tetramethyl-10-phenyl-
3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (6c):[11c]
1H NMR (400 MHz, CDCl3) δ: 7.57 (d, J＝6.8 Hz, 3H),
7.37－7.31 (m, 4H), 7.23 (d, J＝6.0 Hz, 2H), 5,24 (s,
1H), 2.22－2.06 (m, 6H), 1.82 (d, J＝17.2 Hz, 2H),
0.94 (s, 6H), 0.80 (s, 6H).
10-(4-Methoxyphenyl)-3,3,6,6-tetramethyl-9-(p-tolyl)-
3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (6d):[11d]
1H NMR (400 MHz, CDCl3) δ: 7.30 (d, J＝8.0 Hz, 2H),
7.13 (d, J＝8.0 Hz, 2H), 7.04 (d, J＝7.6 Hz, 4H), 5.23
(s, 1H), 3.91 (s, 3H), 2.25 (s, 3H), 2.21－2.05 (m, 6H),
1.85 (d, J＝17.2 Hz, 2H), 0.94 (s, 6H), 0.81 (s, 6H).
9-(4-Chlorophenyl)-10-(4-methoxyphenyl)-3,3,6,6-
tetramethyl-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-
dione (6e):[11d] 1H NMR (400 MHz, CDCl3) δ: 7.36 (d,
J＝8.0 Hz, 2H), 7.21 (d, J＝8.4 Hz, 2H), 7.11 (d, J＝
(4-(4-Bromophenyl)-1-phenyl-1,4-dihydropyridine-
3,5-diyl)bis(phenylmethanone) (4i):[3h] 1H NMR (400
MHz, CDCl3) δ: 7.54 (d, J＝6.8 Hz, 4H), 7.48 (d, J＝
7.2 Hz, 2H), 7.46－7.39 (m, 9H), 7.28 (d, J＝9.2 Hz,
4H), 7.14 (d, J＝8.0 Hz, 2H), 5.65 (s, 1H).
(4-(4-Chlorophenyl)-1-phenyl-1,4-dihydropyridine-
3,5-diyl)bis((4-methoxyphenyl)methanone) (4j): Yellow
1
solid; m.p. 197－199 ℃; H NMR (400 MHz, CDCl3)
δ: 7.57 (d, J＝8.4 Hz, 4H), 7.41 (t, J＝7.6 Hz, 4H), 7.31
(s, 2H), 7.27－7.21 (m, 3H), 7.17 (d, J＝7.6 Hz, 2H),
6.89 (d, J＝8.0 Hz, 4H), 5.66 (s, 1H), 3.82 (s, 6H); 13C
NMR (100 MHz, CDCl3) δ: 193.5, 162.3, 144.3, 143.1,
138.2, 132.2, 131.3, 130.8, 130.2, 129.6, 128.6, 126.8,
Chin. J. Chem. 2015, 33, 568—572
© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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569

Cao et al.
FULL PAPER
8.8 Hz, 2H), 7.04 (d, J＝7.6 Hz, 2H), 5.23 (s, 1H), 3.92
(s, 3H), 2.22－2.05 (m, 6H), 1.85 (d, J＝17.6 Hz, 2H),
0.95 (s, 6H), 0.80 (s, 6H).
10-(4-Chlorophenyl)-3,3,6,6-tetramethyl-9-(p-tolyl)-
3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione (6f):[11e]
1H NMR (400 MHz, CDCl3) δ: 7.54 (d, J＝6.8 Hz, 2H),
7.28 (d, J＝7.6 Hz, 2H), 7.20 (d, J＝6.8 Hz, 2H), 7.04
(d, J＝6.4 Hz, 2H), 5.22 (s, 1H), 2.25 (s, 3H), 2.22－
2.04 (m, 6H), 1.81 (d, J＝17.2 Hz, 2H), 0.95 (s, 6H),
0.81 (s, 6H).
hand, in entries comparing different natural bio-based
catalysts such as L-tyrosine and lactic acid (LA), even
better yield was acquired when LA was used (Table 1,
Entries 6, 7). In subsequent experiments of varying the
catalyst loading, 50 mol% turned out to be proper (Ta-
ble 1, Entries 8, 9). Finally, further increasing the reac-
tion time led to no more positive impact on the product
yield (Table 1, Entry 10).
With the results provided by optimization experi-
ments, the application scope of this green synthetic pro-
tocol was subsequently investigated. Based on the ex-
periments in this section (Table 2), the present protocol
tolerated well to the synthesis of 1,4-DHPs bearing dif-
ferent substitutions (4a－4m) such as alkyl, alkoxyl and
different halogens. Generally, the 1,4-DHPs were af-
forded with moderate to good yield, and no evident ef-
fect of the functional groups in any of the substrates on
the yield of corresponding product was reflected.
Results and Discussion
Firstly, the three-component reaction of dimethyl-
amino functionalized enaminone (1a), p-chloro-
benzaldehyde (2a) and p-methylaniline (3a) was con-
ducted in water in the presence of L-proline from which
the 1,4-DHP 4a was obtained in 19% yield (Table 1,
Entry 1). Heating the reaction to reflux and increasing
the reaction duration both helped to enhance the yield
(Table 1, Entries 2, 3). Attempt in employing
Et3NCH2PhCl or (n-Bu)4NOH as additive did not pro-
vide positive result (Table 1, Entries 4, 5). On the other
Table 2 Synthesis of 1,4-DHPs via three-component reaction
involving N,N-dimethylamino enaminones
O
LA/H2O
2
+
R1
CHO
+
NH2
Ar
N
reflux
Table 1 Optimization on reaction conditionsa
R2
1
3
2
O
CHO
NH2
Ar
N
Cat/water
T
O
2
+
+
1a
N
Cl
R2
R1
3a
2a
O
Ph
Ar
4
O
N
Cl
Ar
Ph
Ph
Ph
Ph
R1
R2
Product Yielda/%
O
4-Cl
2-Cl
4-Cl
H
4-Me
H
4a
4b
4c
4d
4e
4f
61
65
71
61
67
68
64
56
66
71
60
63
65
Ph
4a
Entry
1
Catalyst
T/℃
90
t/h
12
12
20
20
20
20
20
20
20
24
Yieldb/%
19
H
4-Me
4-Me
H
L-Proline
L-Proline
L-Proline
L-Proline
L-Proline
L-Tyrosine
LA
4-MeC6H4
4-MeC6H4
4-Cl
4-Cl
H
2
110
110
110
110
110
110
110
110
110
25
3
27
4c
5d
6
23
4-MeOC6H4
4-Me
H
4g
4h
4i
4-FC6H4
H
27
Ph
4-Br
4-Cl
H
54
4-MeOC6H4
H
4j
7
61
8e
9f
LA
26
Ph
Ph
Ph
4-MeOC6H4 4-MeOC6H4
4k
4l
4-MeC6H4
4-ClC6H4
3-ClC6H4
LA
58
4-MeOC6H4
4m
10
LA
59
a Yield of isolated product based on 1.
a Unless otherwise specified, the reaction conditions are: enami-
none 1a (0.5 mmol), aldehyde 2a (0.3 mmol), amine 3a (0.3
mmol) and catalyst (50 mol%) in 2 mL water, stirred at sealed
Inspired by the successful synthesis of 1,4-DHPs 4
in the sustainable catalytic system consisting of water
and LA, we then attempted to expand its application to
the synthesis of other types of 1,4-DHPs (Scheme 1).
Therefore, the reaction of NH-functionalized cyclic
b
c
tube. Yield of isolated products base on 1a. 50 mol%
Et3NCH2PhCl was added additionally. d 50 mol% (n-Bu)4NOH
was added. e 30 mol% LA was employed. f The LA was 75%
mmol.
570
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Chin. J. Chem. 2015, 33, 568—572

Versatile Synthesis of 1,4-Dihydropyridines via Multicomponent Reactions
Scheme 1 Multicomponent synthesis of polycyclic 1,4-DHPs (the yields are calculated on isolated product based on enaminone 5)
O
Ar1
O
O
O
LA/water
reflux
Ar1 CHO
+
+
N
NH
Ar2
2
HN
Ar2
Ar2
5
6
5
Br
O
O
O
O
O
O
N
N
N
6a, 87%
6b, 85%
6c, 91 %
Cl
O
O
O
O
O
O
N
N
N
OMe
OMe
Cl
6d, 88%
6e, 90%
6f
, 85%
GJJ13245), the Open Research Project from College of
Basic Medical Sciences, Zhejiang Chinese Medical
University and a Innovative Program of Graduate Stu-
dents of Jiangxi Province (No. YC2014-S158).
enaminone 5 was subjected with aldehyde under the
standard reaction conditions for the potential synthesis
of polycyclic 1,4-DHPs of type 6. To our delight, it was
found that the present method was also well applicable
for the synthesis of the 1,4-DHPs 6. In the entries em-
ploying different aryl aldehydes as reaction partners, the
1,4-DHPs 6a－6f were provided with generally excel-
lent yields. This results, together with synthesis of
1,4-DHPs of type 4, clearly demonstrated the broad ap-
plication scope of the green H2O/LA catalytic system in
the synthesis of useful 1,4-DHPs. Meanwhile, when
alkyl aldehyde was employed, no expect formation of
corresponding 4-alkyl 1,4-DHP was observed.
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Conclusions
In conclusion, we have developed an environmen-
tally benign catalytic method for the synthesis of dif-
ferent types of 1,4-DHPs. The catalytic conditions using
water as medium and LA as catalyst represent a new
environmentally friendly methods in the area of
1,4-DHPs synthesis. It can be reasonably useful to com-
plement those previously known protocols towards
1,4-DHPs synthesis.
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Acknowledgement
The present work is financially supported by the
Department of Education of Jiangxi Province (No.
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