Cinchona alkaloid and di-: Tert -butyldicarbonate-DMAP promoted efficient synthesis of (E)-nitroolefins

Article abstract of DOI:10.1039/c6ra06644e

The synthesis of nitroolefins from aldehydes and olefins is generally limited by the formation of a mixture of cis and trans compounds. Here we report an alternative, metal-free protocol for the synthesis of β-nitroolefins from arylidinemalononitrile using cinchona alkaloid along with di-tert-butyldicarbonate-DMAP in high yields with total selectivity.

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Cinchona alkaloid and di-tert-butyldicarbonate-DMAP promoted
efficient synthesis of (E)-nitroolefins
Nataraj Poomathi,a and Paramasivan T. Perumal*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
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synthesis of nitroolefins with an easy to handle metal free reagent
is yet to be developed. Notably, from a practical aspect, metal-free
synthesis9 ( Figure 1) are preferred, as the removal of metal
contamination can render a process quite expensive.10 In particular,
preparation of nitrostyrene under metal-free conditions would be
of great significance due to its close association with the
pharmaceutical industry. To date, only a few synthetic methods
using bifunctional catalysts have been reported, such as those
applying transition metal catalyst and bifunctional catalyst.11 To
Synthesis of nitroolefins from aldehyde and olefin is generally
limited by the formation of mixture of cis and trans compounds.
Here we report an alternative, metal- free protocol for the
synthesis of β-nitroolefins from arylidinemalononitrile using
cinchona alkaloid along with di-tert-butyldicarbonate-DMAP in
high yields with total selectivity.
Nitroolefins are prominent class of synthetic intermediates, which
have found wide application in the preparation of variety of
biorelevant compounds and pharmaceuticals.1 These are widely
used in different carbon-carbon bond-forming reactions like
Michael reaction,2 cycloaddition,3 Morita-Baylis-Hillman reaction,4
and for the generation of oximes,5 hydroxylamines, nitroalkanes6
and aliphatic amines. These are usually synthesized by Henry
reaction, involving base mediated condensation of nitroalkanes
with aldehyde or ketones followed by dehydration.7a,b An
alternative and relatively simple approach relies upon readily
available aldehyde, malononitrile and nitromethane as the strating
materials, wherein anion formation and subsequent β-elimination
of malononitrile lead to the desi-red nitroolefins in a stereoselective
manner. This convenient and step economical process has drawn
significant attention in recent decades.7c,d To date, a number of
methods have been developed with different metal based and
gaseous nitrating agents. 8 These methods while offering significant
improvements in direct nitration of olefins often have several
drawbacks. Problematic issues include the tendency to form an un-
desired mixture of E/Z isomers,8a,b lack of functional group
tolerance,8e,g and harsh reaction conditions among others.8d,g
achieve
the
Michael
addition
of
nitromethane
to
arylidinemalononitrile, we planned to use thiourea and cinchona
alkaloid as a catalyst, where these catalyst systems are able to
“intramolecularise” the reactions via simultaneous activation of two
reaction partners.12a-d To our knowledge, no reports are available
on the β-elimination of malononitrile using cinchona alkaloid and
di-tert-butyldicarbonate leading to the desired nitroolefins. This has
now been relished in the case of aromatic/heteroaromatic using
malononitrile, nitromethane, di-tert-butyldicarbonate, DMAP and
catalytic amount of cinchona alkaloid, This newly developed
method is operationally simple, functional group tolerant, good
yielding and scalable.
Although a number of methods8h-s for the synthesis of nitroolefins
have been developed, more environmentally benign and efficient
approaches are still needed to reduce the use of expensive
catalysts, solvents and toxic reagents. Further, stereoselective
a.Organic Chemistry Division, CSIR-Central Leather Research Institute, Adyar,
Chennai-6000 20, India.
Figure 1 Metal-free strategy for the synthesis of β-nitroolefins.
Fax: +91-44-24911589; E-mail: ptperumal@gmail.com
†Electronic Supplementary Information (ESI) available: Copies of 1H NMR, and 13C
NMR spectra of all compounds and Experimental procedure. See
DOI: 10.1039/x0xx00000x
Initially,
a feasibility study of our hypothesis revealed that
arylidinemalononitrile 1b, nitromethane 2 was investigated using
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Table 1 Optimization of the reaction conditionsc
R
R
Di-tert-butyldicarbonate
NO2
R
CN
CN
Catalyst
NC
CH3NO2
NO2
DMAP, 45-50 deg,
Step-2
Solvents
rt
CN
6b
2
1b
3b
Step-1
Catalysts:
Entry
Catalyst (mol %)
Time (h)
Temp (°C)
Yield (%)
DCMa,b
--
CH3CNa,b
--
Toluenea,b
Dioxanea,b
1.
2.
A (10)
B (10)
C (10)
D (10)
E (10)
F (10)
G (10)
H (10)
F (10)
F (10)
F (10)
--
4
4
50
50
50
50
50
50
50
50
50
50
rt
--
--
--
--
--
--
3.
4
--
--
--
--
4.
4
55
65
78
60
68
77
77
--
45
35
40
35
37
40
40
--
72
62
87
70
75
87
87
--
35
25
35
25
26
30
30
--
5.
4
6.
4
7.
4
8.
4
9.
7
10.
11.
12.
13.
14.
15.
16.
17.
18.
10
10
10
15
4
50
50
60
70
50
50
50
30
40
65
60
70
78
77
30
32
40
35
35
40
40
30
30
83
68
80
87
87
25
25
35
20
30
35
33
--
F (10)
F (10)
F (5)
4
4
F (15)
4
F (25)
4
aThe reaction was performed with arylidinemalononitile 1b (0.1 mmol), nitromethane 2 (0.5 mmole), catalyst, di-tert-butyldicarbonate (0.2 mmol) and DMAP (0.02
mmol) in 2 mL of solvents at 45-50 deg.b Isolated yields. cE/Z ratio is approximately >97/3 for all the synthesized products except entry 6, 8-17 in table 1(E/Z ratio:
99>1). It was determined by NMR analysis of the crude products.
various bases, such as TEA, DABCO, Piperidine , DBU and DMAP
with di-tert butyldicarbonate using catalyst A-H. Although
product 6b can be generated in the presence of all of these bases
except entry 1, 2 and 3, only DMAP resulted in a high chemical
yield using catalyst F in toluene at 45-50 deg to furnish the
desired product 6b in 87 % yield (Table 1, entry 6). Next, several
bifunctional catalysts with different solvents such as CH3CN,
DCM, toluene and dioxane, were evaluated for their efficacy in
this cascade reaction (Table 1, entries 1-18) and cinchona
alkaloid F was found to be the most promising catalyst for this
cascade reaction (Table 1, entry 6). The results showed that
toluene was optimal choice (Table 1, entry 6). However, in the
absence of catalyst, the cascade process did not proceed
significantly, even in toluene (Table 1, entry 12, 13). Finally, we
examined the effect of the catalyst concentration on this cascade
reaction. The results revealed that decreasing the amount of
catalyst F from 10 to 5 mol % led to an decrease in the yield from
87 to 80 % (Table 1, entry 16), whereas by increasing the amount
of catalyst F from 10 to 25 mol %, the yield of the product could
not be improved significantly (Table 1, entry 17, 18). We found
that 2 equiv of di-tert-butyldicarbonate and 10 mol % of catalyst
then investigated to show the generality of this cascade reaction
(Table 2). In most cases, the reactions afforded the
corresponding nitroolefins product with moderate to good yields
(65-90 %). The structural variation of alkylidenemalononitrile 1
could be well tolerated in this reaction irrespective of the
electronic nature or the positions of the substituent on the
aromatic ring, compared with the 4-methoxy benzaldehyde (6e,
90 %) gave excellent yields of the desired nitro product.
It is noteworthy that this cascade process could also be
successfully extended to several 2-formylphenoxy-methyl-3-
phenylacrylate derivatives (Table 2, 6j-6u with including those
containing Cl, Br, Me and OMe) under the optimized conditions
in good yields (70-90 %). The scope of the reaction was further
studied with various heterocyclic compounds under optimized
conditions. Oxgen, sulphur and nitrogen based heterocycles such
as furan, thiophene and indole gave the nitro products (Table 2,
6(v-x)) in 75, 79 and 82
%
isolated yield, respectively.
(e.g 2-
Unfortunately alkylidinemalononitrile
butylidinemalononitrile) did not form the desired nitroolefin
product under the reaction conditions.
°
F in toluene at 50 C could provide β-nitrostyrene in an excellent
90 % isolated yield with complete E-selectivity ( Table 2, 6e).
With the reaction conditions optimized, the substrate scope was
To demonstrate the scalability of the β-elimination of
malononitrile method, 4-chlorobenzaldehyde was reacted in a 6
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Table 2 Substrate scope of the arylidinemalononitriles, 2-formylphenoxy-methyl-3-phenylacrylates and heterocyclic compound in the metal-free synthesis
of β-nitroolefinsa,b
NO2
NO2
NO2
NO2
NO2
NO2
NO2
NO2
NO2
Br
O
NO2
Cl
Br
Br
O
O
NO2
6g, 60 %
OMe
Me
Cl
Cl
6f, 66 %
6h, 63%
6i, 73%
6d, 86 %
NO2
6a, 80 %
6e, 90 %
6b, 87 %
6c, 85 %
6j, 81%
NO2
NO2
NO2
NO2
NO2
NO2
Cl
Br
Cl
Cl
Cl
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
MeO
Cl
Me
Me
Cl
MeO
6m, 88 %
6q, 75 %
6p, 72 %
6l, 70 %
6o, 81 %
6n, 78 %
6k, 83 %
NO2
NO2
NO2
NO2
NO2
NO2
NO2
Br
Br
O
O
O
O
O
O
O
O
N
O
O
O
O
S
O
O
O
6w, 79 %
6v, 75 %
Cl
Cl
6t, 74 %
6x, 82 %
Me
MeO
6r, 81 %
6u, 82 %
6s, 86 %
aUnless otherwise noted, the reactions in step-1 were performed with arylidinemalononitile/2-formylphenoxy-methyl-3-phenylacrylates/heterocyclic compounds
1
(0.1 mmol), nitromethane 2 (0.5 mmole) and catalyst-F (10 mol %). In step-2, the reactions were performed with di-tert-butyldicarbonate (0.2 mmol) and DMAP
(0.02 mmol) in 2 mL of toluene. Yield refers to the column purified products. b E/Z ratio is >99/1 for all the synthesized products. It was determined by NMR analysis
of the crude product
N
N
O
O
O
CO2
N
O
O
O
O
O
N
OMe
N
NC
R
CN
O
N
R
CN
CN
O
CH3NO2
OH
O
N
H
O
N
1
2
H
3
Isolated
N
O
O
N
R
NC
NC
R
CN
N
CN
N
R
O
H
O
H
O
O
NC
CH2
Ph
Ph
NC
H
8
CN
CN
H
N
CN
H
O2N
CN
H
N
O
O
R
O
H
O2N
(E)
N
6
MeO
5
Ph
H
H
H
H
H
NC
NC
H
O2N
CN
CN
R
CN
Ph
Ph
7
O2N
Z
(
)
CN
O2N
N
O
O
H
(Not formed)
H
O
N
N
MeO
5'
Scheme 1 Plausible reaction mechanism for the metal-free synthesis of β-nitroolefins
6
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mmol scale. In this experiment, the desired nitrostyrene product
was isolated in preoperatively useful yield (87 %). The structures
of all the nitroolefins 6(a-u) and 6(v-x) are deduced by their
satisfactory spectral (1H NMR, 13C NMR and EI-HRMS) studies.
The structures of the compounds 6t have been further confirmed
by X-ray analysis13 (Figure 2).
organocatalyst and Boc-anhydride/DMAP combination provides a
better elimination protocol compared to other conventional
base-mediated conditions, without cinchona alkaloid, the overall
yield of the product was found to be very low and E/Z selectivity
also reduced16 which provided further support to the proposed
mechanism. Finally, the absolute (E) configuration was obtained
in accordance with X-ray crystal structure analysis.
Conclusions
In summary, we have described an easy, efficient and metal-
free general route to aromatic β-nitrostyrens with total E-
selectivity has been discovered under mild conditions. The
substrate scope of the arylidinemalononitrile bearing
aromatic and heterocyclic moieties was explored and E-nitro
compounds were obtained selectively. The process is
practical, avoiding multistep and expensive purification
procedure. Further studies are in progress to broaden the
potentiality of the procedure and to better clarify the
reaction pathway.
Figure 2 ORTEP diagram of compound 6t
On the basis of the above results a plausible mechanism for the
formation of β-nitroolefins is proposed in scheme 1. The first
step is the generation of tert-butoxide from DMAP and di-tert-
butyldicarbonate, and which has been proposed previously by
our group.12e Cinchona catalyst F containing hydrogen bond
donors and a tertiary amine moiety, where the amine could be
oriented in such a way as to cooperatively bind a single proton
from the nitromethane and the hydroxyl group could activate
arylidinemalononitrile 1 electrophilically via hydrogen bonding
that would result in efficient assembly of the nitromethane and
the arylidinemalononitrile followed by smooth Michael addition
and consecutive protonation led to the 2-(2-nitro-1-
phenylethyl)malononitrile intermediate 3. We have isolated
intermediate 3u in table 1, which was fully characterized by NMR
spectroscopy.14 Next, in the presence of the generated tert-
Experimental Section
General procedure for the synthesis of Arylidinemalononitriles
and
(E)-methyl-2-((4-chloro-2-(2,2di-cyanovinyl)-phenoxy)-
methyl)-3-(4-methoxy-phenyl)-acrylate derivatives:
Aldehyde (1 mmol), malononitrile (1 mmol) in ethanol (3 mL) and
catalytic amount of water were charged in a 25 mL round
bottomed flask and the resulting solution was stirred for 3-5 h at
room temperature. The consumption of the starting material was
monitored by TLC. The precipitated solid was filtred and washed
with ethanol (5-7 mL), dried under vacuum to obtain pure 1a-x
in good yields (78-89 %). The identities of products were
confirmed by NMR giving good agreement with the assigned
structures.
butoxide, intermediate
3 can be deprotonated to furnish
cabanion 4, which could be possible two conformations 5 and 5’,
stabilized by an hydrogen bonding with catalyst F. The
conformations of which are nearly ideal for the subsequent E2 or
E1cb reaction process for stereo electronic reasons as depicted in
Newman projection 5 and 5’, however intermediate 5’ suffers
from severe steric and more dipole repulsion between Phenyl,
nitro, cyano groups and catalyst F so out of two possible
pathways involving 4, preferential formation of energetically
General procedure for the preparation of E-nitroolefin
derivatives:
A mixture of arylidine/heteroarylidinemalononitriles/(E)-methyl
2-((4-chloro-2-(2,2-di-cyanovinyl)-phenoxy)-methyl)-3-(4-
methox-yphenyl)-acrylate derivatives 1(a-x) (0.1 mmol),
nitromethane 2 (0.5 mmol) in toluene (3 mL) and catalytic
amount of cinchona alkaloid F (10 mol %) were charged in a 25
mL round bottomed flask and the resulting solution was stirred
for 2-5 h at room temperature. The consumption of the starting
material was monitored by TLC. After completition of the
reaction, DMAP (0.020 mmol) and di-tert-butyldicarbonate (2.0
equiv) was then added to a stirred solution of corresponding
crude product 3. After stirring the reaction at 45-50 deg. for 2-3
hrs followed by TLC, the solvent was removed under reduced
pressure and the residue was purified by column
chromatography on siliga gel (3:97 % ethylacetate and petether)
to afford pure products 6(a-x) in average to good yields 65-90 %.
more favourable conformation of intermediate
5 over 5′,
followed by β-elimination of malononitrile to afford the desired
nitro product 6 and recycles malononitrile 8 in scheme 1. The
presence of a single isomer is probably the tertiary amine and
hydroxyl group in cinchona alkaloid would activate the nitro
group (intermediate-4) through hydrogen bonding, thus the
synergistic interactions would ensure high stereoselectivity in
this transformation.15
According to the above plausible reaction mechanism and the
experimental results, this protocol offers greatly improved the
overall yield and E/Z selectivity, is this due to the participation of
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The identities of products 6(a-x) were confirmed by NMR and EI-
HRMS, giving good agreement with the assigned structures.
Elemental analysis: Anal. Calcd for C8H6BrNO2: C, 42.13; H, 2.65;
Br, 35.04; N, 6.14; O, 14.03 %. Found: C, 42.19; H, 2.69; Br, 35.01;
N, 6.19; O, 14.07 %.
6a: (E)-(2-nitrovinyl) benzene: Isolated as yellow solid, 80 %,
m.p: 57-58οC, 1H NMR (400 MHz, CDCl3) δ H 7.93 (1 H, d, J = 13.7),
7.51 (1 H, d, J = 13.7), 7.49 – 7.45 (2 H, m), 7.44 – 7.34 (3 H, m)
6g: (E)-1-nitro-3-(2-nitrovinyl) benzene Isolated as yellow solid,
1
60 %, m.p: 127-128οC, H NMR δ (500 MHz, ) 8.28–8.09 (3 H,
H
ppm. 13C NMR δ (100 MHz, CDCl3) 139.08, 137.15, 132.16,
m), 7.61 (1 H, dd, J = 4.9, 2.2). ppm. 13C NMR δ C (125 MHz, CDCl3)
126.66, 126.39, 130.88, 131.97, 134.67, 148.95 ppm. EI-HRMS:
Anal. Calcd for C8 H6 N2O4: 194.0328 Found: 194.0327. Elemental
analysis: Anal. Calcd for C8H6N2O4: C, 49.49; H, 3.12; N, 14.43; O,
32.96 %. Found: C, 49.43; H, 3.17; N, 14.39; O, 32.91 %.
C
130.10, 129.42, 129.16 ppm. EI-HRMS: Anal. Calcd for C8H7NO2:
149.0477, Found: 149.0472. Elemental analysis: Anal. Calcd for
C8H7NO2 : C, 64.42; H, 4.73; N, 9.39; O, 21.45 %. Found: C, 64.36;
H, 4.79; N, 9.33; O, 21.49 %.
6b: (E)-1-chloro-4-(2-nitrovinyl) benzene: Isolated as yellow
solid, 87 %, m.p: 111-112οC, 1H NMR (400 MHz, CDCl3) δ H 7.96 (1
H, d, J = 13.7), 7.57 (1 H, d, J = 13.7), 7.53 – 7.47 (2 H, m), 7.47 –
7.40 (2 H, m) ppm. 13C NMR (101 MHz, CDCl3) δ C 138.36, 137.71,
137.45, 130.29, 129.79, 128.55 ppm. EI-HRMS: Anal. Calcd for
C8H6ClNO2: 183.0087, Found: 183.0083. Elemental analysis: Anal.
Calcd for C8H6ClNO2 : C, 52.34; H, 3.29; Cl, 19.31; N, 7.63; O,
17.43 %. Found: C, 52.30; H, 3.25; Cl, 19.38; N, 7.68; O, 17.37 %.
6h: (E)-1-bromo-4-(2-nitrovinyl) benzene: Isolated as yellow
solid, 63 %, m.p: 143-145οC, δ H (500 MHz,) 7.94 (1 H, d, J = 13.7),
7.58 (3 H, t, J = 10.8), 7.41 (2 H, d, J = 8.4) ppm. 13C NMR δ C (125
MHz, CDCl3) 127.01, 129.13, 130.60, 132.95, 137.64,138.09 ppm.
EI-HRMS: Anal. Calcd for C8 H6 BrNO2: 226.9582 Found:
226.9580. Elemental analysis: Anal. Calcd for C8H6Br NO2: C,
42.13; H, 2.65; Br, 35.04; N, 6.14; O, 14.03 %. Found: C, 42.09; H,
2.60; Br, 35.09; N, 6.10; O, 13.03 %.
6c: (E)-2,4-dichloro-1-(2-nitrovinyl)benzene: Isolated as yellow
solid, 85 %, m.p: 118-119οC, 1H NMR δ H (400 MHz, CDCl3) 8.33 (1
H, d, J = 13.7), 7.58 (1 H, d, J = 13.7), 7.55 – 7.49 (2 H, m), 7.34 (1
6i: (E)-2-(2-nitrovinyl)naphthalene: Isolated as yellow solid, 73
%, m.p: 128-130οC, 1H NMR δ H (400 MHz, CDCl3) 8.79 (1 H, d, J =
13.4), 8.09 (1 H, d, J = 8.4), 7.98 (1 H, d, J = 8.2), 7.94 – 7.85 (1 H,
m), 7.71 (1 H, d, J = 7.2), 7.66 – 7.54 (3 H, m), 7.53 – 7.46 (1 H, m)
H, dd, J = 8.4, 1.9) ppm. 13C NMR δ (101 MHz, CDCl3) 139.05,
C
ppm. 13C NMR δ (100 MHz, CDCl3) 138.50, 136.09, 133.79,
138.49, 136.68, 133.99, 130.69, 129.29, 128.04, 127.12 ppm. EI-
HRMS: Anal. Calcd for C8 H5 Cl2 NO2: 216.9697, Found: 216.9695.
Elemental analysis: Anal. Calcd for C8 H5 Cl2 NO2: C, 44.07; H,
2.31; Cl, 32.52; N, 6.42; O, 14.68 %. Found: C, 44.0; H, 2.37; Cl,
32.45; N, 6.35; O, 14.61 %.
C
132.58, 131.59, 129.09, 127.76, 126.98, 126.82, 126.41, 125.43,
122.98 ppm. EI-HRMS: Anal. Calcd for C12 H9 NO2: 199.0633,
Found: 199.0632. Elemental analysis: Anal. Calcd for C12H9NO2: C,
72.35; H, 4.55; N, 7.03; O, 16.06 %. Found: C, 72.30; H, 4.47; N,
6.05; O, 16.01 %.
6d: (E)-1-methyl-4-(2-nitrovinyl) benzene: Isolated as yellow
solid, 86 %, m.p: 105-106οC, 1H NMR δ H (400 MHz, CDCl3) 7.98 (1
H, d, J = 13.6), 7.56 (1 H, d, J = 13.6), 7.44 (2 H, d, J = 8.1), 7.25 (2
6j: (E)-methyl 2-((4-bromo-2-((E)-2-nitrovinyl)phenoxy)methyl)-
3-phenylacrylate: Isolated as yellow solid, 81 %, m.p: 98-100οC,
1H NMR δ H (400 MHz, CDCl3) 8.11 (1 H, s), 7.99 (1 H, d, J = 13.7),
7.71 (1 H, d, J = 13.7), 7.58 (1 H, d, J = 2.4), 7.51 (1 H, d, J = 2.5),
7.39 (5 H, s), 6.88 (1 H, d, J = 8.9), 4.99 (2 H, s), 3.89 (3 H, s). 13C
H, d, J = 8.0), 2.41 (3 H, s) ppm. 13C NMR δ (100 MHz, CDCl3)
C
143.14, 139.20, 136.31, 130.17, 129.22, 127.31, 21.68 ppm. EI-
HRMS: Anal. Calcd for C9H9NO2: 163.0633, Found: 163.0630.
Elemental analysis: Anal. Calcd for C9H9NO2: C, 66.25; H, 5.56; N,
8.58; O, 19.61 %. Found: C, 66.20; H, 5.60; N, 8.51; O, 19.69 %.
NMR δ (100 MHz, CDCl3) 167.19, 157.14, 146.43, 139.11,
C
135.62, 134.12, 134.07, 133.57, 129.95, 129.40, 128.92, 126.08,
121.63, 114.77, 113.73, 64.07, 52.59 ppm. EI-HRMS: Anal. Calcd
for C19 H16 Br NO5: 417.0212, Found: 417.0210. Elemental
analysis: Anal. Calcd for C19H16BrNO5: C, 54.56; H, 3.86; Br, 19.10;
N, 3.35; O, 19.13 %. Found: C, 54.51; H, 3.82; Br, 18.70; N, 3.31;
O, 18.15 %.
6e: (E)-1-methoxy-4-(2-nitrovinyl) benzene: Isolated as yellow
solid, 90 %, m.p: 90-92οC, 1H NMR δ H (400 MHz, CDCl3) 7.96 (1 H,
d, J = 13.6), 7.52 (1 H, d, J = 6.0), 7.51–7.48 (2 H, m), 6.99–6.92 (2
H, m), 3.86 (3 H, s) ppm. 13C NMR δ (100 MHz, CDCl3) 162.99,
C
139.07, 135.02, 131.21, 122.55, 114.95, 55.55 ppm. EI-HRMS:
Anal. Calcd for C9 H9 NO3: 179.0582, Found: 179.0580. Elemental
analysis: Anal. Calcd for C9H9NO3: C, 60.33; H, 5.06; N, 7.82; O,
26.79 %. Found: C, 60.39; H, 5.01; N, 7.75; O, 26.73 %.
6k:(E)-methyl-2-((2-((E)-2-nitro-vinyl)-phenoxy)-methyl)-3-
phenyl-acrylate: Isolated as yellow solid, 83 %, m.p: 127-130οC,
1H NMR δ H (400 MHz, CDCl3) 8.11 (1 H, t, J = 6.8), 7.78 (1 H, d, J =
13.6), 7.50 – 7.40 (2 H, m), 7.39 – 7.36 (1 H, m), 7.05 (1 H, t, J =
7.5), 6.99 (1 H, d, J = 8.4), 5.01 (1 H, s), 3.89 (2 H, s). 13C NMR δ C
(100 MHz, CDCl3) 167.34, 158.28, 146.22, 138.34, 135.28, 134.19,
133.38, 132.34, 129.84, 129.48, 128.88, 126.40, 121.62, 119.70,
112.96, 63.67, 52.55 ppm. EI-HRMS: Anal. Calcd for C19 H17 NO5:
339.1107, Found: 339.1105. Elemental analysis: Anal. Calcd for
6f: (E)-1-bromo-2-(2-nitrovinyl) benzene: Isolated as yellow
solid, 66 %, m.p: 140-142οC, 1H NMR δ H (400 MHz, CDCl3) 8.40 (1
H, d, J = 13.7), 7.69 (1 H, dd, J = 7.8, 1.4), 7.63 – 7.49 (2 H, m),
7.44–7.26 (2 H, m) ppm. 13C NMR δ (100 MHz, CDCl3) 138.89,
C
137.60, 134.04, 132.92, 130.41, 128.49, 128.08, 126.35 ppm. EI-
HRMS: Anal. Calcd for C8 H6 Br NO2: 226. 9582 Found: 226.9581.
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C19H17NO5: C, 67.25; H, 5.05; N, 4.13; O, 23.57 %. Found: C, 67.17;
H, 5.01; N, 4.19; O, 23.51 %.
136-138οC, H NMR δ H (400 MHz, CDCl3) 8.15 (1 H, s), 7.97 (1 H,
d, J = 13.7), 7.69 (1 H, d, J = 13.7), 7.47 – 7.39 (2 H, m), 7.33 (3 H,
ddd, J = 8.6, 5.4, 2.0), 7.29–7.22 (1 H, m), 6.86 (1 H, d, J = 8.9),
6l: (E)-methyl 2-((4-chloro-2-((E)-2-nitrovinyl)phenoxy)methyl)-
3-(4-chlorophenyl)acrylate: Isolated as yellow solid, 70 %, m.p:
135-137οC, 1H NMR δ H (400 MHz, CDCl3) 7.98–7.87 (1 H, m), 7.62
(1 H, d, J = 13.7), 7.37 (1 H, d, J = 2.5), 7.32–7.22 (3 H, m), 6.87 (1
4.91 (2 H, s), 3.91 (3 H, s) ppm. 13C NMR δ (100 MHz, CDCl3)
C
166.60, 156.47, 142.93, 139.03, 134.25, 133.54, 132.86, 132.71,
130.93, 130.85, 129.98, 129.90, 128.18, 127.02, 126.73, 121.12,
114.47, 64.34, 52.71ppm. EI-HRMS: Anal. Calcd for C19 H15 Cl2
NO5: 407.0327, Found: 407.0325. Elemental analysis: Anal. Calcd
for C19H15Cl2NO5: C, 55.90; H, 3.70; Cl, 17.37; N, 3.43; O, 19.60 %.
Found: C, 55.84; H, 3.64; Cl, 17.31; N, 3.49; O, 19.53 %.
H, d, J = 8.9), 4.88 (1 H, s), 3.81 (2 H, s). 13C NMR δ (100 MHz,
C
CDCl3) 166.95, 156.49, 145.02, 139.06, 136.18, 133.51, 132.80,
132.47, 131.04, 130.69, 129.23, 126.85, 126.61, 121.11, 114.38,
64.02, 52.67 ppm. EI-HRMS: Anal. Calcd for C19 H15 Cl2 NO5:
407.0327, Found: 407.0325. Elemental analysis: Anal. Calcd for
C19H15Cl2NO5: C, 55.90; H, 3.70; Cl, 17.37; N, 3.43; O, 19.60 %.
Found: C, 55.85; H, 3.66; Cl, 17.31; N, 3.49; O, 19.55 %.
6q: (E)-methyl 2-((4-chloro-2-((E)-2-nitrovinyl)phenoxy)methyl)-
3-(p-tolyl)acrylate: Isolated as yellow solid, 75 %, m.p: 149-
151οC, H NMR δ (400 MHz, CDCl3) 8.09–7.94 (1 H, m), 7.72 (1
1
H
H, d, J = 13.7), 7.43 (1 H, d, J = 2.6), 7.37 (1 H, dd, J = 8.9, 2.6),
7.30 (1 H, d, J = 8.1), 7.20 (1 H, d, J = 8.0), 6.95 (1 H, d, J = 8.9),
6m: (E)-methyl-3-(4-methoxy-phenyl)-2-((2-((E)-2-nitro-vinyl)-
phenoxy)-methyl)-acrylate: Isolated as yellow solid, 88 %, m.p:
108-110οC, 1H NMR δ H (400 MHz, CDCl3) 8.24–8.01 (1 H, m), 7.77
(1 H, d, J = 13.6), 7.52–7.35 (2 H, m), 7.09–6.98 (1 H, m), 6.90 (1
H, d, J = 8.8), 5.04 (1 H, s), 3.87 (1 H, s), 3.81 (1 H, s). 13C NMR δ C
(100 MHz, CDCl3) 167.67, 161.12, 158.36, 146.17, 138.31, 135.30,
133.42, 132.34, 131.67, 126.66, 123.78, 121.57, 119.70, 114.40,
112.99, 63.82, 55.38, 52.42 ppm. EI-HRMS: Anal. Calcd for C20 H19
NO6: 369.1212, Found: 369.1211. Elemental analysis: Anal. Calcd
for C20H19NO6: C, 65.03; H, 5.18; N, 3.79; O, 25.99 %. Found: C,
64.06; H, 5.12; N, 3.72; O, 26.06 %.
5.00 (1 H, s), 3.88 (2 H, s), 2.36 (2 H, s) ppm. 13C NMR δ (100
C
MHz, CDCl3) 167.38, 156.71, 146.59, 140.52, 139.12, 133.71,
132.72, 131.23, 131.19, 129.67, 129.58, 126.58, 125.07, 121.13,
114.40, 64.21, 52.51, 21.41ppm. EI-HRMS: Anal. Calcd for C20 H18
Cl NO5: 387.0874, Found: 387.0873. Elemental analysis: Anal.
Calcd for C20H18ClNO5: C, 61.94; H, 4.68; Cl, 9.14; N, 3.61; O,
20.63 %. Found: C, 61.99; H, 4.61; Cl, 9.19; N, 3.52; O, 20.55 %.
6r: (E)-methyl 2-((4-bromo-2-((E)-2-nitrovinyl)phenoxy)methyl)-
3-(4-chlorophenyl)acrylate: Isolated as yellow solid, 81 %, m.p:
133-135οC, 1H NMR δ H (400 MHz, CDCl3) 8.06–7.96 (1 H, m), 7.69
(1 H, d, J = 13.7), 7.59 (1 H, d, J = 2.4), 7.52 (1 H, dd, J = 8.8, 2.4),
7.41–7.30 (2 H, m), 6.89 (1 H, d, J = 8.9), 4.95 (1 H, s), 3.89 (2 H, s)
6n: (E)-methyl 2-((4-bromo-2-((E)-2-nitrovinyl)phenoxy)methyl)-
3-(p-tolyl)acrylate: Isolated as yellow solid, 78 %, m.p: 123-
140οC, H NMR δ (400 MHz, CDCl3) 8.14–7.92 (1 H, m), 7.71 (1
ppm. 13C NMR δ (100 MHz, CDCl3) 166.93, 156.97, 145.06,
1
H
C
H, d, J = 13.6), 7.58 (1 H, d, J = 2.4), 7.50 (1 H, dd, J = 8.8, 2.5),
7.33–7.25 (1 H, m), 7.20 (1 H, d, J = 8.0), 6.90 (1 H, d, J = 8.9),
139.06, 136.21, 135.70, 134.02, 133.42, 132.45, 130.68, 129.24,
126.57, 121.60, 114.73, 113.95, 63.94, 52.68 ppm. EI-HRMS:
Anal. Calcd for C19 H15 Br Cl NO5: 450.9822, Found: 450.9820.
Elemental analysis: Anal. Calcd for C19H15BrClNO5: C, 50.41; H,
3.34; Br, 17.65; Cl, 7.83; N, 3.09; O, 17.67 %. Found: C, 50.35; H,
3.30; Br, 17.69; Cl, 7.88; N, 3.02; O, 17.61 %.
5.00 (1 H, s), 3.88 (2 H, s), 2.36 (2 H, s) ppm. 13C NMR δ (100
C
MHz, CDCl3) 167.36, 157.19, 146.61, 140.53, 139.11, 135.62,
134.15, 133.61, 131.22, 129.67, 129.58, 125.03, 121.62, 114.77,
113.66, 64.14, 52.52, 21.41ppm. EI-HRMS: Anal. Calcd for C20 H18
Br NO5: 431.0368, Found: 431.0366. Elemental analysis: Anal.
Calcd for C20H18BrNO5: C, 55.57; H, 4.20; Br, 18.48; N, 3.24; O,
18.51 %. Found: C, 55.51; H, 4.17; Br, 18.43; N, 3.29; O, 18.43 %.
6s: (E)-methyl 2-((4-bromo-2-((E)-2-nitrovinyl)phenoxy)methyl)-
3-(4-methoxyphenyl)acrylate: Isolated as yellow solid, 81 %,
1
m.p: 148-150οC, H NMR δ (400 MHz, CDCl3) 8.05 (1 H, s), 7.99
H
6o: (E)-methyl 2-((4-chloro-2-((E)-2-nitrovinyl)phenoxy)methyl)-
3-(4-methoxyphenyl)acrylate: Isolated as yellow solid, 81 %,
m.p: 140-142οC, 1H NMR δ H (400 MHz, CDCl3) 8.08–7.96 (1 H, m),
7.71 (1 H, d, J = 13.7), 7.44 (1 H, d, J = 2.6), 7.39 (1 H, dd, J = 8.9,
2.7), 7.00 (1 H, d, J = 8.9), 6.91 (1 H, d, J = 8.8), 5.03 (1 H, s), 3.87
(1 H, s), 3.82 (2 H, s) ppm. 13C NMR δ C (100 MHz, CDCl3) 167.57,
161.20, 156.74, 146.37, 139.11, 133.72, 132.76, 131.63, 131.18,
126.59, 126.53, 123.45, 121.13, 114.44, 114.42, 64.30, 55.40,
52.46 ppm. EI-HRMS: Anal. Calcd for C20 H18 Cl NO6: 403.0823,
Found: 403.0822. Elemental analysis: Anal. Calcd for C20H18ClNO6:
C, 59.49; H, 4.49; Cl, 8.78; N, 3.47; O, 23.77 %. Found: C, 59.43; H,
4.42; Cl, 8.74; N, 3.54; O, 23.70 %.
(1 H, d, J = 13.7), 7.70 (1 H, d, J = 13.6), 7.57 (1 H, d, J = 2.4), 7.51
(1 H, dd, J = 8.8, 2.4), 7.38 (2 H, d, J = 8.7), 6.92 (3 H, dd, J = 16.2,
8.8), 5.02 (2 H, s), 3.87 (3 H, s), 3.82 (3 H, s) ppm. 13 C NMR: δ
C
(100 MHz, CDCl3) 167.55, 161.20, 157.22, 146.37, 139.08, 135.67,
134.12, 133.61, 131.64, 126.51, 123.41, 121.61, 114.81, 114.45,
113.66, 64.24, 55.40, 52.46 ppm. EI-HRMS: Anal. Calcd for C20 H18
Br NO6: 447.0317, Found: 447.0315. Elemental analysis: Anal.
Calcd for C20H18BrNO6: C, 53.59; H, 4.05; Br, 17.83; N, 3.12; O,
21.42 %. Found: C, 53.51; H, 4.01; Br, 17.89; N, 3.05; O, 21.35 %.
6t:(E)-methyl-3-(2-chloro-phenyl)-2-((2-((E)-2-nitrovinyl)-
phenoxy)-methyl)-acrylate: Isolated as yellow solid, 86 %, m.p:
1
125-128οC, HNMR δ (400 MHz, CDCl3) 8.16 (1 H, s), 8.08 (1 H,
H
6p:(E)-methyl2-((4-chloro-2-((E)-2-nitrovinyl)phenoxy)methyl)-
3-(2-chloro-phenyl)-acrylate: Isolated as yellow solid, 72 %, m.p:
d, J = 13.6), 7.75 (1 H, d, J = 13.6), 7.49–7.36 (4 H, m), 7.32 (1 H,
m), 7.26–7.20 (1 H, m), 7.04 (1 H, t, J = 7.6), 6.92 (1 H, d, J = 8.4),
6 | J. Name., 2012, 00, 1-3
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4.92 (2 H, s), 3.92 (3 H, s) ppm. C NMR: δ (100 MHz, CDCl3)
Women Scientist Fellowship under women scientist scheme
(WOS-A) and SAIF IITM Chennai for EI-HRMS analysis.
C
166.72, 156.52, 142.71, 141.53, 135.12, 134.88, 133.33, 132.05,
131.78, 130.74, 130.09, 129.83, 128.89, 128.46, 128.00, 126.99,
125.12, 121.69, 113.84, 113.03, 63.88, 49.48 ppm. EI-HRMS:
Anal. Calcd for C19 H16 Cl NO5: 373.0717, Found: 373.0715.
Elemental analysis: Anal. Calcd for C19H16ClNO5: C, 61.05; H, 4.31;
Cl, 9.48; N, 3.75; O, 21.40 %. Found: C, 61.0; H, 4.25; Cl, 9.42; N,
3.70; O, 21.33 %.
Notes and references
1
(a) A. G. M. Barret and G. G. Graboski, Chem. Rev., 1986,
86, 751; (b) P. Talalay, M. J. Delong and H. Prochaska, J.
Proc. Natl. Acad. Sci. U.S.A. 1988, 85, 8261; (c) T. A. Alston,
D. J. T. Porter and H. Bright, J. Bioorg. Chem., 1985, 13
,
375; (d) P. Cheng, Z. Y. Jiang, R. R. Wang, X. M. Zhang, Q.
Wang, Y. T. Zheng, J. Zhou and J. J. Chen, Bioorg. Med.
Chem. Lett., 2007, 17, 4476; (e) S. Kaap, I. Quentin, D.
Tamiru, M. Shaheen, K. Eger and H. Steinfelder, J.
Biochem. Pharmacol., 2003, 65, 603; (f) J. H. Kim, G. E. Lee,
J. E. Lee and I. K. Chung, Mol. Pharmacol., 2003, 63, 1117;
(g) H. Uehara, R. Imashiro, G. Hernandez-Torres and C. F.
Barbas, Proc. Natl. Acad. Sci. U.S.A. 2010, 107, 20672; (h)
Y. Meah and V. Massey, Proc. Natl. Acad. Sci. U.S.A. 2000,
97, 10733; (i) K. Sakai, A. Nakazawa, K. Kondo and H. Ohta,
Agric. Biol. Chem,., 1985, 49, 2331; (j) M. A. Reddy, N. Jain,
D. Yada, C. Kishore, V. J. Reddy, P. S. Reddy, A. Addlagatta,
6u: (E)-methyl 2-((2-((E)-2-nitrovinyl)phenoxy)methyl)-3-(p-
tolyl)acrylate: Isolated as yellow solid, 82 %, m.p: 118-120οC,
1HNMR (400 MHz, CDCl3) δ H 8.10 (1 H, d, J = 14.8), 7.77 (1 H, d, J
= 13.6), 7.44 (1 H, dd, J = 18.4, 8.0), 7.32 (1 H, d, J = 7.8), 7.25 (1
H, t, J = 7.5), 7.18 (2 H, d, J = 7.4), 7.03 (1 H, dd, J = 17.7, 8.1),
13
5.02 (1 H, s), 3.88 (2 H, s), 2.35 (3 H, s) ppm. NMR: δ (100
C
MHz, CDCl3) 167.50, 158.34, 146.36, 140.36, 138.34, 135.27,
133.35, 132.32, 131.35, 129.64, 129.62, 129.05, 128.23, 125.41,
125.31, 121.57, 119.72, 112.99, 63.76, 52.46, 21.39 ppm. EI-
HRMS: Anal. Calcd for C20 H19 NO5: 353.1263, Found: 353.1260.
Elemental analysis: Anal. Calcd for C20H19NO5: C, 67.98; H, 5.42;
N, 3.96; O, 22.64 %. Found: C, 67.91; H, 5.48; N, 3.90; O, 22.60 %.
S. V. Kalivendi and B. Sreedhar, J. Med. Chem., 2011, 54
,
6751; (k) L. Q. Lu, J. R. Chen and W. Xiao, J. Acc. Chem.
Res., 2012, 45, 1278.
2
3
(a) T. Ishii, S. Fujioka, Y. Sekiguchi and H. Kotsuki, J. Am.
Chem. Soc., 2004, 126, 9558; (b) H. B. Huang and E. N.
Jacobsen, J. Am. Chem. Soc,. 2006, 128, 7170; (c) C. B.
6v: (E)-3-(2-nitrovinyl) furan : Isolated as yellow solid, 75 %, m.p:
74-76οC, 1H NMR δ (400 MHz, CDCl3) 7.94 (1 H, d, J = 13.5),
H
Tripathi, S. Kayal and S. Mukherjee, Org. Lett., 2012, 14
3296.
,
7.84–7.83 (1 H, m), 7.52 (1 H, t, J = 1.3), 7.41 (1 H, s), 7.37 (1 H, s),
7.26 (1 H, s), 6.57 (1 H, d, J = 1.9). 13C NMR δ (100 MHz, CDCl3)
(a) D. A. Evans, S. Mito and D. Seidel, J. Am. Chem. Soc.,
2007, 129 11583; (b) J. March, Advanced Organic
C
,
147.29, 145.37, 136.74, 129.53, 118.21, 107.25 ppm. EI-HRMS:
Anal. Calcd for C6 H6 NO3: 139.0269, Found: 139.0267. Elemental
analysis: Anal. Calcd for C6H6NO3: C, 51.80; H, 3.62; N, 10.07; O,
34.50 %. Found: C, 51.74; H, 3.67; N, 10.01; O, 34.45 %.
Chemistry, 3rd ed.; John Wiley & Sons: New York, 1985; (c)
R. C. Larock, Comprehensive Organic Transformations;
VCH: New York, 1989; (d) L. Albrecht, G. Dickmeiss, F. C.
Acosta, C. Rodriguez-Escrich, R. L. Davis and K. A.
Jorgensen, J. Am. Chem. Soc., 2012, 134, 2543; (e) Y. K.
Liu, M. Nappi, E. Arceo, S. Vera and P. Melchiorre, J. Am.
Chem. Soc., 2011, 133, 15212; (f) T. Arai, A. Mishiro, N.
Yokoyama, K. Suzuki and H. Sato, J. Am. Chem. Soc,. 2010,
132, 5338; (g) S. E. Denmark and A. Thorarensen, Chem.
Rev., 1996, 96, 137.
6w: (E)-3-(2-nitrovinyl) thiophene: Isolated as yellow solid, 89 %,
m.p: 87-90οC, 1H NMR δ H (400 MHz, CDCl3) 8.15 (1 H, d, J = 13.4),
7.57 (1 H, d, J = 4.9), 7.51–7.43 (2 H, m), 7.15 (1 H, dd, J = 5.1,
3.7). 13C NMR
δ
(100 MHz, CDCl3) 135.39, 134.62, 133.79,
C
4
(a) D. Basavaiah, B. S. Reddy and S. S. Badsara, Chem. Rev.,
2010, 110, 5447; (b) D. K. Nair, S. M. Mobin and I. N. N.
Namboothiri, Org. Lett., 2012, 14, 4580.
A. Corma, P. Serna and H. Garcia, J. Am. Chem. Soc., 2007,
129, 6358.
N. J. A. Martin, L. Ozores and B. List, J. Am. Chem. Soc.,
2007, 129, 8976.
(a) R. Ballini and G. Bosica, J. Org. Chem., 1997, 62, 425;
(b) S. Fioravanti, L. Pellacani, P. A. Tardella and M. C.
Vergari, Org. Lett., 2008, 10, 1449; (c) P. A. Clarke, S.
132.09, 131.63, 128.90 ppm. EI-HRMS: Anal. Calcd for C6H5NO2S:
155.0041, Found: 155.0040. Elemental analysis: Anal. Calcd for
C6H5NO2S: C, 46.44; H, 3.25; N, 9.03; O, 20.62; S, 20.66 %. Found:
C, 46.40; H, 3.21; N, 9.09; O, 20.55; S, 20.60 %.
5
6
7
6x:(E)-tert-butyl-3-(2-nitro-vinyl)-1H-indole-1-carboxylate:
Isolated as yellow solid, 89 %, 1H NMR : δ H (400 MHz, CDCl3) 8.23
(1 H, d, J = 8.1), 8.17 (1 H, d, J = 13.7), 8.03 (1 H, s), 7.78 (1 H, d, J
= 13.7), 7.71 (1 H, dd, J = 7.2, 0.8), 7.41 (2 H, dtd, J = 20.7, 7.4,
Santos and W. H. C. Martin, Green Chem., 2007, 9, 438; (d)
J. P. Wan, Y. Lin, Q. Huang and Y. Liu, J. Org. Chem., 2014,
79, 7232.
1.2), 1.70 (9 H, s) ppm. 13C NMR: δ (100 MHz, CDCl3) 148.63,
C
136.40, 135.79, 132.19, 131.58, 126.85, 125.97, 124.26, 120.20,
115.93, 112.51, 85.58, 28.10 ppm. EI-HRMS: Anal. Calcd for C15
H16 N2 O4: 288.1110, Found: 288.1109. Elemental analysis: Anal.
Calcd for C15H16N2O4: C, 62.49; H, 5.59; N, 9.72; O, 22.20; %.
Found: C, 62.42; H, 5.53; N, 9.79; O, 22.14; %.
8
(a) P. K. Kancharla, Y. S. Reddy, S. Dharuman and Y. D.
Vankar, J. Org. Chem., 2011, 76, 5832; (b) I. Jovel, S.
Prateeptongkum, R. Jackstell, N. Vogl, C. Weckbecker and
M. Beller, Adv. Synth. Catal., 2008, 350, 2493; (c) P. J.
Campos, B. Garcia and M. A. Rodriguez, Tetrahedron Lett.,
2000, 41, 979; (d) H. Suzuki and T. Mori, J. Org. Chem.,
1997, 62, 6498; (e) T. Mukaiyama, E. Hata and T. Yamada,
Chem. Lett., 1995, 505. (f) W. W. Sy and A. W. By,
Tetrahedron Lett., 1985, 26, 1193; (g) R. S. Varma, K. P.
Naicker and P. J. Liesen, Tetrahedron Lett., 1998, 39, 3977;
(h) E. Hata, T. Yamada and Mukaiyama, Bull. Chem. Soc.
Acknowledgements
One of the authors N. Poomathi, thanks to the Department of
Science and Technology (DST), New Delhi for the award of the
This journal is © The Royal Society of Chemistry 20xx
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DOI: 10.1039/C6RA06644E
COMMUNICATION
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102.1556(12) deg., c = 14.6295(4) A gamma = 90 deg:
14 3u:(E)-methyl-2-((2-(1,1-di-cyano-3-nitro-propan-2-yl)-
phenoxy)-methyl)-3-(p-tolyl)-acrylate: Isolated as yellow
gelly semi solid, 95 %, H NMR (400 MHz, CDCl3) 8.00 (1H,
1
s), 7.36–7.22 (3H, m), 7.19 (3H, t, J = 8.0), 6.97 (1H, t, J =
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13
dd, J = 14.3, 8.7), 3.82 (3H, s), 2.32 (3H, s) ppm. C NMR:
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13 Crystal data for product 6t (CCDC-:1051895, Figure 2): C19
H16ClNO5, crystallised in the monoclinic, space group P
2(1)/n with the following unit cell parameters a =
8 | J. Name., 2012, 00, 1-3
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RSC Advances
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DOI: 10.1039/C6RA06644E
Abstract:
Synthesis of nitroolefins from aldehyde and olefin is generally limited by the formation of
mixture of cis and trans compounds. Here we report an alternative, metal- free protocol for the
synthesis of β-nitroolefins from arylidinemalanonitrile using bifunctional cinchona alkaloid
along with di-tert-butyldicarbonate-DMAP in high yields with total selectivity

RSC Advances
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DOI: 10.1039/C6RA06644E