Oxidative Olefination of Benzylamine with an Active Methylene Compound Mediated by Hypervalent Iodine (III)

Article abstract of DOI:10.1002/ejoc.201900970

Hypervalent iodine-mediated oxidative olefination of amines with an active methylene compound provides a rapid gateway towards the formation of electrophilic alkenes under mild reaction conditions in good to excellent yields. This is an efficient protocol for the preparation of substituted electrophilic alkenes.

Full text of DOI:10.1002/ejoc.201900970

A Journal of
Accepted Article
Title: Hypervalent Iodine (III) Mediated Oxidative Olefination of
Benzylamine with an Active Methylene Compound
Authors: Bapurao Rupanawar, Sruthi M Veetil, and Gurunath Mallappa
Suryavanshi
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201900970
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10.1002/ejoc.201900970
European Journal of Organic Chemistry
FULL PAPER
Hypervalent Iodine (III) Mediated Oxidative Olefination of
Benzylamine with an Active Methylene Compound
Bapurao D. Rupanawar,[ab] Sruthi M. V.[c] and Gurunath Suryavanshi* [ab]
Abstract: Hypervalent iodine-mediated oxidative olefination of
amines with an active methylene compound provides a rapid
gateway towards the formation of electrophilic alkenes under mild
reaction conditions in good to excellent yields. This is an efficient
protocol for the preparation of substituted electrophilic alkenes. .
MSK/RSK-family kinase, [2d]. WP1130, a small molecule derived
from a compound with Janus-activated kinase inhibitory activity.
Degrasyn (WP1130) is a selective deubiquitinase, Entacapone
is used in Parkinson disease and antiviral activities [2e-f]
.
Due to the enormous range of applications of these electrophilic
alkenes, the development of new and efficient methods for the
oxidative olefination is a topic of significant research interest. In
literature, there are several routes for the synthesis of
electrophilic alkenes are well-known with aldehydes or ketones
Introduction
[3]
with active methylene compound using organocatalysts, ionic
[4]
The oxidative olefination is one of the most powerful tools for the
synthesis of substituted electrophilic alkenes via C–C bond
formation. Oxidative olefination of benzylamine and active
methylene groups lead to the formations of the motifs like esters,
amides and nitriles. These motifs are not only synthetically
important, but also act as useful and productive functional
groups in chemical transformations. The transformation of nitrile
to amine, amide and aldehydes; and from ester to acids,
alcohols and aldehyde are the useful chemical transformations
using the above motifs. Also, these moieties can be used as
Michael acceptor and dienophile in a Diels-Alder reaction[1a-l].
liquids
and metal-based. catalysts including Lewis acids,
bases [5], MOFs [6] and nanocatalysts. [7]
However, for the selective conversion of 2-benzylidene
[8]
malononitrile to amides, both homogenous
and
(Ru (OH)x
[9a]
heterogeneous catalysts such as (Au/TiO2),
[9b]
[9c]
/Al2O3),
(Ag/HAP),
used extensively.More recently, our
group reported
a
direct method for the synthesis of 2-
cyanoacrylamides by the condensation and selective mono-
hydration of nitrile starting from aldehyde and malononitrile in
the presence of “TfOH; [10]
Figure1. Drug candidates having cyanoacrylamide moieties
Moreover, highly substituted 2-cyanoacrylamides and their
derivatives are not only distinctive structural frameworks, but
also shows significant biological activities. Substituted 2-
[2a]
cyanoacrylamides act as protein kinase inhibitor,
GTPase
[2b]
[2c]
Scheme 1: Synthesis of electrophilic olefin via oxidative olefination Reaction
inhibitor,
galactokinase inhibitor,
Pre-functionalized
cyanoacrylamide have shown promising inhibitory activities for
In the past decade, organic chemist have attracted towards
condensation of amine with active methylene compound to form
electrophilic alkenes. The main challenge associated with
nucleophilic amines that undergo polarity inversion to form
electrophilic imine and it is further useful for oxidative olefination
with various active methylene compounds. So far there are only
two reports available for the oxidative olefination of amines. In
2013, X. Zeng and co-worker report oxidative olefination of N-
methyl benzylamines with carbon nucleophiles such as
acetophenone by using stoichiometric amount (NH4)2S2O8
(Scheme 1).[11] Further in the same year in 2013, Tian and co-
workers described the oxidative olefination of N-phenyl
[a]
Bapurao D. Rupanawar. Dr.Gurunath Suryavanshi.
Chemical Engineering & Process Development Division, CSIR-
National Chemical Laboratory, Dr. Homi Bhaba Road, Pashan,
Pune- 411008, Maharashtra, India.
Tel: +912025902547.Fax:+912025902676, E-mail:
gm.suryavanshi@ncl.res.in
Bapurao D. Rupanawar. Dr.Gurunath Suryavanshi.
Academy of Scientifc and Innovative Research (AcSIR),
Ghaziabad, Uttar Pradesh 201002.
[b]
[c]
Sruthi M.V.
Central NMR Facility, CSIR-National Chemical Laboratory,
Dr.Homi Bhaba Road, Pashan, Pune- 411008, Maharashtra, India
Supporting information for this article is given via a link at the end
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10.1002/ejoc.201900970
European Journal of Organic Chemistry
FULL PAPER
benzylamines with carbon nucleophiles such as 2- and 4-methyl
pyridine, quinoline, isoquinoline, malononitrile as substrate by
using stoichiometric amount of DDQ. [12]
of PIDA, we observed 80% yield of the desired product 3a (entry
3). When we increased the concentration of oxidant from 1
equivalent to 2 equivalents, no further improvement in the yield
was observed (entry 4). Also, we examined the reaction with
other sources of hypervalent iodine i.e PIFA which offered 52%
yield of desired product (entry 5). When reaction was performed
in absence of oxidant reaction failed to give product (entry 14),
which indicates that oxidant is essential for olefination to form
the desired product. Next, we decreased the concentration of
oxidant from 1 equivalent to 0.5 equivalents for 45 min. we got
3a in 43% yield. Only the PIDA provided the desired product 3a
in 60% to 80% yield. To check the feasibility of solvent, we
performed reaction in various solvents. After careful evaluation,
it was observed that aprotic as well as protic solvents such as
toluene, DMSO, dioxane, THF, DMF and EtOH were less
effective to carry out reaction and affords the corresponding
product 3a in 30% to 60% yield (entries 6-13). When the
reaction was performed in dichloromethane provided the high
yield (78%) of desired product (entry 6). After detailed
optimization study, we were pleased to find that reaction
proceeds very well with PIDA (1 mmol%) in acetonitrile as well
as in dichloromethane solvent (Table 1, entries 3 and 8).
However, these reactions have some limitations, such as
corresponding products were formed when secondary amine
reacted under reaction conditions and fails in case of primary
amines. Apart from this, reaction have some more limitations like
harsh reaction conditions, longer reaction time, and they are
selectively only for N-Phenyl or N-Methyl benzylamines
(Scheme1). Considering the importance of 2-cyanoacrylamide
and electrophilic olefins and as a part of our ongoing research in
the development of new synthetic methodologies and organic
transformations over metal free condition
reporting the PIDA-mediated oxidative olefination of
[13]
herein, we are
benzylamine,
cyanoacetamide,
dibenzylamine,
malononitrile
tribenzylamine
with
the
and ethylcyanoacetate
respectively to form electrophilic alkenes under mild reaction
condition in good to excellent yield.
Results and Discussion
After having the optimized reaction condition in hand
Initially, we instigated our investigation employing commercially
available benzylamine 1a with cynoacetamide 2a in the
presence of PIDA (1 equivalent) as an oxidant in CH3CN solvent
at room temperature for 5 min under N2 atmosphere.
and keeping the importance of acetamide in mind we explored
the substrate scope of the present method for the synthesis of
substituted acrylamide Various substituted aryl amines 1a were
reacted with the cyanoacetamide 2a under optimised reaction
conditions giving good to excellent yields of desired acrylamides
(Table2, entries 3a-3q). Initially, unsubstituted aromatic amines
(1a-1b) i.e. benzyl amine and 1-napthylamine were reacted with
cyanoacetamide 2a under the optimized reaction condition, to
provide the 2-cyanoacrylamide desired product 3a and 3b in
80% and 72% yield respectively (Table 2). To check the effect of
electronic substitution, we subjected various benzyl amines with
electron donating as well as withdrawing groups under optimised
reaction conditions. It is noteworthy that, electron donating
groups such as Me, OMe gives highest yields of product despite
the position of substituent (3c-d and 3g-h), whereas electron
withdrawing group such as NO2, Cl gives moderate yields of the
desired product compared to electron donating group
respectively (3e-f and 3i-k). The disubstituted benzylamines
gave the corresponding acrylamides in good to moderate yield
regardless to substitution. (3l-m). The hydroxyl protected
benzylamines such as piperonylamine and 2,3-dihydro-1,4-
benzodioxin-6-ylmethylamine gives corresponding acrylamides
in good yields (3n-o). Interestingly, heterocyclic amine such as
furfurylamine (1q) subjected under our optimized reaction
condition to give desired product 3q in 63% yield. The (E)-
stereoselectivities of 2-cyanoacrylamides products were
confirmed using NOESY experiment of substrate 3e (see ESI†).
Further, to explore the potential of our methodology, the reaction
was carried out with malononitrile and ethyl 2-cyanoacetate with
substituted benzylamine. As expected, we obtained the
corresponding substituted 2-benzylidenemalononitrile and ethyl-
2-cyano-3-phenylacrylate in 90 and 81% yield respectively. This
reaction is practically remarkable with substituted benzylamines
(1c-e, 1g-i) such as OMe, Me, Cl and NO2 irrespective to the
position of substitution gives corresponding substituted
benzelidene malononitriles and ethyl-2-cyanoacetate in good to
excellent yields (89-74%) (3t-3zh). Also, furfurylamine (1r)
delivered the desired product 79% and 78% yield when reacted
with malanonitrile and ethyl-2-cyanoacetate under optimised
Table 1. Optimization of Reaction Condition
Sr.No.
Oxidant
(Equiv.)
PIDA(1)
PIDA(1)
PIDA(1)
PIDA(2)
PIFA(1)
PIDA(1)
PIDA(1)
PIDA(1)
PIDA(1)
PIDA(1)
PIDA(1)
PIDA(1)
PIDA(1)
-
Solvent.
Time
(Min.)
Yield b
(%)
54
65
80
81
52
60
52
78
58
30
35
46
31
N.R
20
43
1
2
3
4
5
6
7
8
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
DCE
5 Min
15 Min
45Min
45 Min
45 Min
45 Min
45 Min
45 Min
45 Min
45 Min
45 Min
45 Min
45 Min
45 Min
45 Min
45 Min
EtOH
CH2Cl2
Dioxane
DMF
DMSO
THF
Toluene
CH3CN
CH3CN
CH3CN
9
10
11
12
13
14
15
16
PIDA(0.25)
PIDA(0.50)
aReaction conditions: 1a (1 mmol), 2a (1.2 mmol), oxidant (1mmol), solvent (5
mL), rt, 45 min. under N2 atmosphere. bIsolated yields, N.R = No reaction.
To our delight, the expected product 3a was obtained in 54%
yield (Table 1, entry 1). This initial result inspired us to
investigate the optimized reaction condition for the formation of
3a. It has been observed that there was not much difference in
the yields of the desired product with the increase in time (entry
2). Further the reaction continued for 45 min. using 1 equivalent
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10.1002/ejoc.201900970
European Journal of Organic Chemistry
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reaction
condition
respectively
(3z&zi).
Delightfully,
methylene group. Whereas the time required for completion of
the reaction was 3h. with use of 3 equivalents of oxidant.
benzhydrylamine gave 84% yield of desired product under
standard reaction condition (3zj).
Table 3. Substrate Scope of Dibenzylamines and Tribenzylamines
Table 2. Substrate scope of the amine with various active methylene
compound
However, N-benzylaniline 6a, N-benzyl-N-phenylaniline 6b and
N-benzyl-N-methylaniline 6c failed to give the desired product
3a, 3r and 3za under optimized reaction condition (Table 4).
Also, we have screened different aliphatic amines under
optimized reaction condition, unfortunately reaction failed to give
desired products. Also, active methylene compounds having
ketone or aldehyde functional group fail to give desired product.
Table4. Substrate scope of N- methyl/phenyl benzylamine
We proposed a possible reaction mechanism for the formation of
electrophilic alkenes product (Scheme 2). Initially, benzyl amine
1a react with Iodobenzene diacetate to form intermediate
species 7 further it undergoes deprotonation to form 8 followed
[14a-c
by cyclic state syn elimination to get imine 9
]and
iodobenzene and acetic acid as by product.
aReaction conditions: 4a (1 mmol), 2 (a, b and c) (1.2 mmol), PIDA (1 mmol),
in CH3CN, rt, 45min, under N2 atmosphere.
To check the feasibility of the reaction we thought to perform the
olefination of dibenzylamine 4a under optimised reaction
condition with all three active methylene compounds. As
expected, we need to increase the concentration of oxidant from
1 equivalent to 2 equivalents. The desired products 3a, 3r & 3za
were achieved in 72-80% yield (Table 3). It is noteworthy that,
the rate of reaction gradually decreases and time required for
completion of reaction was 2h. Fortunately, similar reactivity was
observed when tribenzyl amine 5a was reacted with active
Scheme 2. Plausible reaction mechanism
Subsequently, malononitrile 2b undergoes tautomerisation in
acetic acid to form 10 [16] and followed by nucleophillic attack on
imine intermediate 9[17] to form β-amino compound 11 which on
further protonation gives 12. The formed intermediate 12
undergoes E1cB elimination to give 3r with removal of NH3.
Our main goal is to find out in which way our reaction proceeds
via either imine or aldehyde. To verify the proposed mechanism,
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10.1002/ejoc.201900970
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we have carried out time dependent 1H NMR study at 25 °C
Experimental Section
1
temperature in CD3CN. Primarily, the H NMR of benzyl amine
was taken followed by addition of each reagent. Then the 1H
NMR of this reaction mixture was recorded at constant time
difference i.e. after 5 min. It was observed that after addition of
PIDA the peak corresponds to -NH2 of benzyl amine shifts
towards deshielded region of H NMR (δ 3.12). As the time of
reaction increased to the 10 min. the formation of imine 9 was
General Information:
Unless otherwise specified, all reactions were carried out under an open
atmosphere in solvent at room temperatures. All reagents and solvents
were obtained from commercial suppliers and Aldrich, Merck Millipore,
Alfa Aesar and Avra Synthesis. Amines were purified by distillation after
dissolving in ether, prior to use and all AR grade solvents were used
without further purification.
1
Petroleum ether of boiling range 60–80 °C was used. Melting points are
uncorrected. 1H NMR and 13C NMR spectra were recorded on AC-200,
400, 500 MHz NMR spectrometers. Deuterated solvent CDCl3 , DMSO
were used as internal standard. The septet at 2.50 ppm in 1H NMR and
39.51 ppm in 13C NMR corresponds to Hydrogen and carbon of DMSO-
D6. The peaks at 7.27 ppm in 1H NMR and 77.00 ppm in 13C NMR
corresponds to proton and carbon of CDCl3. Infrared (IR) spectra were
recorded on a Fourier transform infrared spectrometer as a thin film.
HRMS data for all new compounds were recorded using Orbitrap mass
analyzer associated with Accela 1250 pump. Purification was done using
column chromatography (100-200 mesh). The reactions were monitored
by TLC visualized by UV (254 nm) and/or with KMnO4.Coupling
constants are given in hertz (Hz) and the classical abbreviations are used
to describe the signal multiplicities.
Typical Experimental Procedure for the Synthesis Compound( 3a-
3zj):
To the solution of amines (1.0 mmol) was added PhI(OAc)2 (1mmol) in 2
mL of CH3CN at 0 ºC and followed by addition of active methylene
compound i.e cyanoacetamide, or malononitrile, or ethylcynoacetate (1.2
mmol). The resulting mixture was stirred at room temperature for 45 min
under N2 atmosphere. The progress of reaction was monitored by TLC.
After completion of reaction the solvent was evaporated under vaccum.
The reaction mixture was quenched by saturated solution of NaHCO3 (5
mL) and extracted with EtOAc (10 mL). The organic layers were
combined, wash with brine and dried over Na2SO4 and concentrated
under reduced pressure. The residue was purified by column
chromatography on silica gel (100-200 mesh) and 10-40% ethyl acetate
in petroleum ether as an eluting solvent to afford the desired product.
Figure 2. Time dependent 1H NMR experiment for Mechanistic Determination
observed (δ 3.85).14b subsequently, the 1H NMR after 20 min
clearly shows a broad singlet at δ 4.29 corresponds to –NH2 of
addition product 10 as shown in Figure 2. It is noteworthy that
the intensity of peak at δ 3.92 decreases constantly. Whereas,
1H NMR at 40 min. shows a very broad peak at δ 4.69
correspond to the –NH3 of intermediate 11[15]. Interestingly, when
1H NMR was recorded at 45 min both the peaks vanished from
1H NMR confirms the elimination of ammonia and acetic acid.
1
From the above time dependent HNMR study, it was confirmed
Typical Experimental Procedure for the Synthesis of 3a, 3r, 3za from
Dibenzyl amine :
that the reaction proceeds via elimination of ammonia and not by
formation of benzaldehyde. It is noteworthy to observe the
formation
of
imine
intermediate
i.e.
N-benzyl-1-
To the solution of amine (1.0 mmol) was added PhI(OAc)2 (2 mmol) in
2mL of CH3CN at ºC and followed by addition of active methylene
compound i.e cyanoacetamide or malononitrile or ethylcynoacetate (2.4
phenylmethanimine was observed in time dependent 1H NMR
experiment of dibenzyl and tribenzyl amine (Please See SI).
°
mmol) at 0 C. The resulting mixture was stirred at room temperature for
2h under N2 atmosphere. The progress of reaction was monitored by
TLC. After completion of reaction the solvent was evaporated under
vaccum. The reaction mixture was quenched by saturated solution of
NaHCO3 (5 mL) and extracted with EtOAc (10 mL). The organic layers
were combined, wash with brine and dried over Na2SO4 and
concentrated under reduced pressure. The residue was purified by
column chromatography on silica gel (100-200 mesh) and 10-40% ethyl
acetate in petroleum ether as an eluting solvent to afford the desired
product.
Conclusions
In summary, we have developed hypervalent iodine mediated
oxidative olefination reaction of benzylamines, dibenzylamine
and tribenzylamine with active methylene compound such as
cyanoacetamide, malononitrile and ethyl cyanoacetate
respectively to form electrophilic alkenes.
The attractive
features of this protocol includes metal-free reaction, shorter
reaction time, mild reaction condition, broad substrate scope,
wide functional group tolerance, and practically remarkable in
terms of yields and scalability. The reaction mechanism was
further assisted with time dependent 1H NMR Spectroscopy.
Application of the present methodology are currently in progress.
Typical Experimental Procedure for the Synthesis of 3a, 3r, 3za from
Tribenzyl amine:
To the solution of amine (1.0 mmol) was added PhI(OAc)2 (3 mmol) in
2mL of CH3CN at ºC and followed by addition of cyanoacetamide , or
malonitrile or ethylcynoacetate (3.6mmol) at 0C. The resulting mixture
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10.1002/ejoc.201900970
European Journal of Organic Chemistry
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was stirred at room temperature for 3h under N2 atmosphere. The
progress of reaction was monitored by TLC. After completion of reaction
the solvent was evaporated under vaccum. The reaction mixture was
quenched by saturated solution of NaHCO3 (5 mL) and extracted with
EtOAc (10 mL). The organic layers were combined, wash with brine and
dried over Na2SO4 and concentrated under reduced pressure. The
residue was purified by column chromatography on silica gel (100-200
mesh) and 10-40% ethyl acetate in petroleum ether as an eluting solvent
to afford the desired product.
1601, 1382, 745, cm-1; HRMS (ESI) calculated [M+H]+ for C10H8 OBrN2:
250.9815; found: 250.9815
(E)-2-cyano-3-(4-methoxyphenyl)acrylamide(3g):
Yellow solid; (Pet. ether /EtOAc = 60/40); Yield: 102 mg, 70%; White
solid; mp: 220 ºC;1H NMR (500 MHz, DMSO-d6): δ 3.86 (br. s., 3H), 7.06
- 7.23 (m, 2H) ,7.67 (br. s., 1H), 7.80 (br. s., 1H), 7.87 - 8.05 (m, 2H),
8.11 (br. s., 1H). 13C NMR (101 MHz, DMSO-d6): δ 55.6, 102.9, 114.8,
117.0, 124.4, 132.4, 150.1, 162.5, 163.1; IR Vmax = 3565, 3178, 2360,
1734, 1510,743, cm-1; HRMS (ESI) calculated [M+H]+ for C11H11O2N2:
203.0815; found: 203.0812
(E)-2-cyano-3-phenylacrylamide (3a):
White solid; (Pet. Ether/EtOAc = 75/25); Yield: 128 mg, 80%; mp: 130
ºC ; 1H NMR: (200 MHz, CDCl3 ): δ 6.58 (br. s., 1H), 6.88 (br. s., 1H),
7.35 - 7.58 (m, 3H), 7.90 (d, J=6.19 Hz, 2H), 8.29 (s, 1H). 13C NMR (50
MHz, CDCl3):δ 103.3,116.8, 129.1, 130.6, 131.5, 132.8, 153.7, 162.45;
IR Vmax = 3336, 3192, 2216, 1672, 1589, 751,685, cm-1; HRMS (ESI)
calculated [M + H]+ for C10H9N2O: 173.0709; found: 173.0707.
(E)-2-cyano-3-(p-tolyl)acrylamide(3h):
White Solid; (Pet. ether /EtOAc = 65/35); Yield: 111 mg, 82%; White
solid; mp: 136 ºC; 1H NMR (500 MHz, CDCl3): δ 2.44 (s, 3H), 6.67 (br. s.,
2H), 7.31 (d, J=8.01 Hz, 2H), 7.87 (d, J=8.01 Hz, 2H), 8.31 (s, 1H). 13
C
NMR (126 MHz, CDCl3): δ 21.82 101.56, 117.2, 128.9, 130.0, 130.9,
144.4, 154.07 , 162.5; IR Vmax = 3388, 3157, 2217, 1693, 1589, 1372,
1214,745,668, cm-1; HRMS (ESI) calculated [M + H]+ for C11H11ON2:
187.0866; found: 187.0864.
(E)-2-cyano-3-(naphthalen-1-yl)acrylamide (3b):
White solid; (Pet. ether / EtOAc = 65/35); Yield: 101 mg, 72%; White
solid; mp: 168 ºC; 1H NMR (400 MHz, DMSO-d6): δ 7.66 (t, J=6.41 Hz,
3H), 7.85 (br. s., 1H), 8.05 (d, J=6.71 Hz, 2H), 8.17 (d, J=8.55 Hz, 1H),
8.13 (d, J=8.55 Hz, 1H), 8.23 (br. s., 1H), 8.89 (s, 1 H). 13C NMR (101
(E)-2-cyano-3-(4-nitrophenyl)acrylamide (3i):
MHz, DMSO-d6):
δ 111.23, 116.09, 123.7, 125.4, 126.8, 127.1,
Yellow Solid; (Pet. ether /EtOAc = 60/40); Yield: 85 mg, 60%; Yellow
solid; mp: 198-200 ºC; 1H NMR (400 MHz, DMSO-d6): δ 7.92 (br. s., 1H),
8.06 (br. s., 1H), 8.12 (d, J=8.55 Hz, 2H), 8.29 (s, 1H), 8.38 (d, J=9.16 Hz,
2H). 13C NMR (101 MHz, DMSO-d6): δ 110.6 ,115.7, 124.2, 131.0, 138.1,
148.3, 148.8, 162.1; ; IR Vmax = 3335, 2323, 1698, 1647, 1509.82, 1020
cm-1; HRMS (ESI) calculated [M + H]+ for C10H8 O3 N3: 218.0566; found:
218.0560.
127.4,128.7, 129.3, 130.7 ,131.8, 132.9, 148.4, 162.6; IR Vmax = 3019,
2360, 1699, 1540, 1710, 744,668, cm-1; HRMS (ESI) calculated
[M+H]+ for C14H11ON2 Na: 245.0685; found: 245.0684.
(E)-2-cyano-3-(2-methoxyphenyl)acrylamide (3c):
Yellow solid; (Pet. ether /EtOAc = 60/40); Yield: 110 mg, 75%; mp: 146-
148 ºC; 1H NMR (400 MHz, DMSO-d6): δ 3.87 (br. s., 3H), 7.02 - 7.22 (m,
2H), 7.56 (t, J=7.63 Hz, 1H), 7.76 (br. s., 1H), 7.89 (br. s., 1H), 7.99 (d,
J=7.32 Hz, 1H), 8.41 (s, 1 H). 13C NMR (101 MHz, DMSO-d6): δ 56.3,
107.0, 112.3, 116.9, 120.9, 121.1, 128.8, 134.6, 146.2, 158.7, 163.0; IR
(E)-2-cyano-3-(4-cyanophenyl)acrylamide(3j):
White Solid; (Pet. Ether/EtOAc = 75/25); Yield: 105 mg, 70%; mp: 146
ºC ; 1H NMR (400 MHz, DMSO-d6): δ 7.90 (br. s., 1 H), 7.94 - 8.19 (m,
5H), 8.25 (s, 1H). 13C NMR (101 MHz, DMSO-d6): δ 109.9, 113.8, 115.8,
118.2, 130.3, 132.9, 136.3, 148.7, 162.1; IR Vmax = 2341, 1691, 1599.82,
1020,745, cm-1; HRMS (ESI) calculated [M + H]+ for C11H8 O N3:
198.0662; found: 198.0639.
Vmax
= 3346 3020, 2215, 1689, 1588, 751, 667, cm-1; HRMS (ESI)
calculated [M+H]+ for C11H11O2N2: 203.0815; found: 203.0816.
(E)-2-cyano-3-(o-tolyl)acrylamide (3d):
White solid; (Pet. ether /EtOAc = 65/35); Yield: 102 mg, 72%; White solid;
mp: 125-127 ºC; 1H NMR (400 MHz, DMSO-d6): δ 2.36 (s, 3H), 7.24 (t,
J=7.02 Hz, 2H), 7.30 - 7.37 (m, 1H), 7.51 (br. s., 2H), 7.87 (d, J=7.93 Hz,
1H), 8.38 (s, 1H). 13C NMR (101 MHz, DMSO-d6): δ 18.2, 106.5,114.9,
124.8 126.5 , 129.3 ,129.8, 130.2, 137.4, 148.6, 161.0; IR Vmax = 3021,
2218, 1684, 1589, 751, cm-1; HRMS (ESI) calculated [M+H]+ for
C11H11ON2: 187.0866; found: 187.0868.
(E)-3-(4-bromophenyl)-2-cyanoacrylamide(3k):
Yellow solid; (Pet. Ether/EtOAc = 75/25); Yield: 98 mg, 68%; mp: 198 ºC;
1H NMR (400 MHz, DMSO-d6): δ 7.90 (br. s., 1H), 8.04 (br. s., 5H), 8.25
(br. s., 1H). 13C NMR (101 MHz, DMSO-d6): δ 107.3, 116.2, 125.9,
131.1, 131.7, 132.3, 149.4, 162.5; IR Vmax = 3437, 3156, 2214, 1698, ,
1591, 1020, 754, cm-1 ; HRMS (ESI) calculated [M + H]+ for C10H8 O N2:
250.9815; found: 250.9815
(E)-3-(2-chlorophenyl)-2-cyanoacrylamide (3e):
(E)-2-cyano-3-(2,4-dichlorophenyl)acrylamide(3l):
White solid; (Pet. ether /EtOAc = 65/35); Yield: 100 mg, 69%; off white
solid; mp: 143 ºC; 1H NMR (400 MHz, DMSO-d6): δ 7.10 (br. s., 1H),
7.31 (br. s., 1H), 7.37 - 7.49 (m, 3H), 8.02 (d, J=7.32 Hz, 1H), 8.52 (s,
1H). 13CNMR (101 MHz, DMSO-d6): δ 108.1 , 115.8 , 127.1 , 129.2,
129.9, 130.1, 132.8, 135.4, 148.52, 161.4; IR Vmax = 3451, 3148, 2360,
1699, 1685, 1591, 1395, 745, cm-1; HRMS (ESI) calculated [M+H]+ for
C10H8 OClN2: 207.0320; found: 207.0317.
White solid; (Pet. Ether/EtOAc = 75/25); Yield: 105 mg, 71%; mp: 125
ºC ; 1H NMR (400 MHz, DMSO-d6): δ 7.65 (d, J=9.16 Hz, 1H), 7.78 - 7.91
(m, 1H), 7.94 (br. s., 1H), 8.01 (d, J=8.54 Hz, 1H), 8.08 (br. s., 1H), 8.30
(s, 1H). 13C NMR (101 MHz, DMSO-d6): δ 111.4, 115.3, 128.1, 129.5,
129.7, 130.9, 135.0, 136.9, 145.9, 161.6; IR Vmax = 2339, 1690, , 1584,
1214, 754, cm-1; HRMS (ESI) calculated [M + H]+ for C10H6N2OCl Na:
262..9749; found: 262..9751.
(E)-3-(2-Bromophenyl)-2-cyanoacrylamide(3f):
(E)-2-cyano-3-(3,5-dimethoxyphenyl)acrylamide (3m):
White solid; (Pet. Ether/EtOAc = 75/25); Yield: 88 mg, 65%; mp: 130 ºC ;
1H NMR (400 MHz, DMSO-d6): δ 7.40 - 7.53 (m, 1H), 7.58 (t, J = 7.63 Hz,
1H), 7.82 (d, J = 7.93 Hz, 1H), 7.94 (d, J = 7.93 Hz, 2H), 8.06 (br. s., 1H),
8.31 (s,1H). 13C NMR (101MHz, DMSO-d6): δ 110.9, 115.4, 124.3, 128.3,
129.9, 132.3, 133.2, 149.7, 161.7; IR Vmax = 3465, 3156, 2339, 1705,
Brown solid; (Pet. Ether/EtOAc = 75/25); Yield: 108 mg, 78%; mp: 170
ºC; 1H NMR (400 MHz, DMSO-d6): δ 3.78 (s, 6 H), 6.71 (br. s., 1H), 7.11
(br. s., 1H), 7.18 (br. s., 1H), 7.42 (br. s, 1H), 7.77 (br. s., 1H), 8.15 (s,
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201900970
European Journal of Organic Chemistry
FULL PAPER
1H). 13C NMR (101 MHz, DMSO-d6): δ 55.5, 104.16107.0, 107.9, 116.4,
133.6, 150.5, 160.6, 162.7; IR Vmax = 3164, 2223, 1721, 1594, 1303,
1165, cm-1; HRMS (ESI) calculated [M + H]+ for C12H13N2O3: 233.0921;
found: 233.0920.
White solid; (Pet. ether /EtOAc = 90/10); Yield: 106mg, 79%; Yellow
solid; mp: 78-80 ºC; 1H NMR (500 MHz, CDCl3): δ 3.92 (s, 3H), 7.00 (d,
J=8.39 Hz, 1H), 7.05 (t, J=7.82 Hz, 1H), 7.53 - 7.62 (m, 1H), 8.14 (dd,
J=8.01, 1.14 Hz, 1H), 8.27 (s, 1H). 13C NMR (126 MHz, CDCl3): δ 55.7,
80.8, 111.4, 112.8, 114.1, 119.8, 120.9, 128.4, 136.4, 154., 158.74; IR
Vmax = 2229, 1584, 1214,, 742, 667, cm-1; HRMS (ESI) calculated [M +
H]+ for C11H9N2O : 185.0709; found: 185.0706.
(E)-3-(benzo[d][1,3]dioxol-5-yl)-2-cyanoacrylamide (3n):
White solid; (Pet. Ether/EtOAc = 75/25); Yield: 114 mg, 80%; mp: 204
ºC ;1H NMR (400 MHz, DMSO-d6): δ 6.17 (br. s., 2H), 7.12 (d, J=7.93 Hz,
1H), 7.48 (d, J=7.32 Hz, 1H), 7.59 (br. s., 1H), 7.69 (br. s., 1H), 7.80 (br.
s., 1H), 8.07 (br. s., 1H). 13C NMR (101 MHz, DMSO-d6): δ 102.3, 103.3,
2-(2-methylbenzylidene)malononitrile(3u):
White solid; (Pet. ether /EtOAc = 90/10); Yield: 120 mg, 86%; Yellow
solid; mp: 107-109 ºC; 1H NMR (500 MHz, CDCl3): δ 2.45 (s, 3H), 7.32 -
7.38 (m, 2H), 7.47 - 7.52 (m, 1H), 8.08 (d, J=8.01 Hz, 1H), 8.12 (s, 1H).
13C NMR (126 MHz, CDCl3): δ 19.6, 83.6, 112.3, 113.6, 126.8, 128.0,
129.7, 131.2, 133.9, 139.6, 158.1; IR Vmax = 2225, 1577, 1481, 1230, 754,
708, 617, cm-1; HRMS (ESI) calculated [M + H]+ for C11H9N2: 169.0760;
found: 169.0759.
107.9, 109.0, 116.9, 125.9, 127.9, 148.0, 150.2, 151.0, 162.9; IR Vmax
=
2210, 1664, 1510,743, cm-1; HRMS (ESI) calculated [M + H]+ for
C11H9N2O3: 217.0608 found: 217.0609.
(E)-2-cyano-3-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)acrylamide(3o):
White solid; (Pet. Ether/EtOAc = 75/25); Yield: 110 mg, 79%; 1H NMR
(400 MHz, DMSO-d6): δ 4.32 (dd, J=15.87, 4.88 Hz, 4H), 7.04 (d, J=8.54
Hz, 1H), 7.42 - 7.51 (m, 1H), 7.52 - 7.61 (m, 1H), 7.69 (br. s., 1H), 7.80
(br. s., 1H), 8.04 (s, 1H). 13C NMR (DMSO-d6): δ 63.9, 64.6, 103.4, 116.9,
117.8, 118.4, 124.9, 125.1, 143.5, 147.3, 150.0, 162.9; IR Vmax = 3202,
2212, 1676, 1576, 1506, 1290, 1065, cm-1; HRMS (ESI) calculated [M
+ H]+ for C12H11N2O3: 231.0764.; found: 231.0764.
2-(2-chlorobenzylidene)malononitrile(3v):
Brown solid; (Pet. ether /EtOAc = 90/10); Yield: 103 mg, 78%; Yellow
solid; mp: 94-96 ºC; 1H NMR (500 MHz, CDCl3): δ 7.42 - 7.49 (m, 1H),
7.54 - 7.57 (m, 2H), 8.18 (d, J=8.01 Hz, 1H), 8.27 (s, 1H). 13C NMR (50
MHz, CDCl3) δ : 85.4, 95.5, 111.1, 112.4, 127.1, 128.5, 128.9, 130.0,
134.3, 135.7, 155.02 ; IR Vmax
= 2223, 1593, 1450, 957, 755, 678, 616
cm-1; HRMS (ESI) calculated [M + H]+ for C10H6ClN2: 189.0214; found:
189.0219.
(E)-2-cyano-3-(3-nitrophenyl)acrylamide(3p):
Brown solid; (Pet. Ether/EtOAc = 75/25); Yield: 93 mg, 65%; mp: 210
ºC; 1H NMR (400 MHz, DMSO-d6): δ 7.84 - 7.91 (m, 2H), 8.01 (br. s., 1H),
8.29 - 8.35 (m, 2H), 8.38 (d, J=7.93 Hz, 1H), 8.76 (br. s., 1H). 13C NMR
(101 MHz, DMSO-d6): δ 109.48, 115.8, 124.1, 126.2, 130.8, 133.4, 135.9,
2-(4-methoxybenzylidene)malononitrile(3w):
Yellow solid; (Pet. ether /EtOAc = 90/10); Yield: 120 mg, 89%; Yellow
solid; mp: 112-114 ºC; 1H NMR (200 MHz, CDCl3): δ 3.93 (s, 3H), 6.84 -
7.16 (m, 2H), 7.65 (s, 1H), 7.73 - 8.03 (m, 2H). 13C NMR (50 MHz,
CDCl3): δ 55.9 81.3, 111.4, 112.9, 114.2, 120.1, 121.1, 128.82 ,136.4,
154.4, 158.9; IR Vmax = 2221, 1579, 1482, 1308, 1252, 1021, 758, 617,
cm-1; HRMS (ESI) calculated [M + H]+ for C11H9N2O: 185.0709; found:
185.0706.
148.0, 148.3, 162.1; IR Vmax
1529,1353,1214,737, cm-1; HRMS (ESI) calculated [M
C10H10NO3: 218.0560; found: 218.0563.
= 3349, 3021, 2219, 1690, 1598,
+
H]+ for
(E)-2-cyano-3-(furan-2-yl)acrylamide (3q):
Yellow solid; (Pet. ether /EtOAc = 60/40); Yield: 105 mg, 63%; Yellow
solid; mp: 148-150 ºC; 1H NMR (400 MHz, DMSO-d6): δ 6.81 (dd, J=3.36,
1.53 Hz, 1H), 7.36 (d, J=3.66 Hz, 1H), 7.70 (br. s., 1H), 7.80 (br. s., 1H),
7.97 (s, 1H), 8.11 (s, 1H). 13C NMR(101 MHz, DMSO-d6): δ 101.2, 113.9,
116.3, 121.4, 135.9, 148.3, 148.6, 162.6; IR Vmax = 3409, 3053, 2213,
2-(4-methylbenzylidene)malononitrile(3x):
Brown solid; (Pet. ether /EtOAc = 90/10); Yield: 118 mg, 85%; Yellow
solid; mp: 130-132 ºC; 1H NMR (400 MHz, CDCl3): δ 2.46 (s, 3H), 7.34 (d,
J=8.39 Hz, 2H), 7.66 - 7.76 (m, 1H), 7.81 (d, J=8.39 Hz, 2 H). 13C NMR
(101 MHz, CDCl3): δ 21.5, 80.5, 112.4, 113.5, 128.0, 129.9, 130.4, 145.9,
159.3; IR Vmax = 2222, 1586, 1215, 746, cm-1; HRMS (ESI) calculated
[M + H]+ for C11H9N2: 169.0760; found: 169.0759.
1697, 1598, 1214, 763,
C8H7O2N2: 163.0502; found: 163.0500.
cm-1; HRMS (ESI) calculated [M+H]+ for
2-benzylidenemalononitrile(3r):
2-(4-nitrobenzylidene)malononitrile(3y):
White solid; (Pet. ether /EtOAc = 90/10); Yield: 123 mg, 90%; Yellow
solid; mp: 80-82 ºC; 1H NMR (200 MHz, CDCl3) δ 7.49 - 7.70 (m, 3H),
7.78 (s, 1H), 7.85 - 8.03 (m, 2H). 13C NMR (50 MHz, CDCl3) : δ 83.5,
113.1, 114.3, 130.2, 131.3, 131.5, 135.2, 160.5 ; IR Vmax = 2225, 1590,
1435,1215, 751, 679, 616 cm-1; HRMS (ESI) calculated [M + H]+ for
C10H7N2: 155.0604; found: 155.0602.
White solid; (Pet. ether /EtOAc = 90/10); Yield: 105 mg, 80%; Yellow
solid; mp: 160-162 ºC; 1H NMR (500 MHz, CDCl3): δ 7.90 (s, 1H), 8.08
(m, J=8.39 Hz, 2H), 8.39 (m, J=8.39 Hz, 2H). 13C NMR (126 MHz,
CDCl3): δ 87.5, 111.6, 112.6, 124.6, 131.34 , 135.8 , 150.3, 156.9; IR
Vmax = 2232, 1521, 1345, 935, 851 cm-1; HRMS (ESI) calculated [M +
H]+ for C10H6N3O2: 200.03818; found: 200.03818.
2-(naphthalen-1-ylmethylene)malononitrile(3s):
2-(furan-2-ylmethylene)malononitrile(3z):
Yellow solid; (Pet. ether /EtOAc = 90/10); Yield: 105 mg, 81%; Yellow
solid; mp: 164-166 ºC; 1H NMR (400 MHz, CDCl3): δ 7.59 - 7.77 (m, 3H),
7.96 (d, J=8.27 Hz, 2H), 8.12 (d, J=8.27 Hz, 1H), 8.28 (d, J=6.76 Hz, 1H),
8.65 (s, 1H). 13C NMR(126 MHz, CDCl3): δ 85.1, 112.4, 113.6, 122.2,
125.3, 127.2, 127.4, 128.4, 128.5, 129.3, 131.0, 133.4, 134.8, 157.6; IR
Vmax = 2223, 1593, 1450, 957, 755, 678, 616 cm-1; HRMS (ESI)
calculated [M + H]+ for C14H9N2: 205.0760; found: 205.0759.
Brown Solid; (Pet. ether /EtOAc = 90/10); Yield: 118 mg, 79%; Yellow
solid; mp: 66-68 ºC; 1H NMR (200 MHz, CDCl3): δ 6.72 (dd, J=3.73, 1.71
Hz, 1H) 7.36 (d, J=3.66 Hz, 1H) 7.53 (s, 1H) 7.81 (d, J=1.39 Hz, 1H). 13
C
NMR (50 MHz, CDCl3): δ 76.3, 112.5, 113.7, 114.3, 123.5, 143.0, 147.9,
149.5; IR Vmax = 2227, 1593, 755, 678, 616 cm-1; HRMS (ESI)
calculated [M + H]+ for C8H5N2O: 145.0396; found: 145.0398.
2-(2-methoxybenzylidene)malononitrile(3t):
Ethyl (E)-2-cyano-3-phenylacrylate(3za):
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10.1002/ejoc.201900970
European Journal of Organic Chemistry
FULL PAPER
White solid; (Pet. ether /EtOAc = 90/10); Yield: 163 mg, 85%; white solid;
J=8.34 Hz, 2H), 8.11 (s, 1H) . 13C NMR (50 MHz, CDCl3): δ 14.1, 21.8,
62.5, 101.5, 115.7, 128.8, 129.9, 131.2, 144.6, 154.9, 162; IR Vmax =
2985, 2217, 1719, 1596, 1268, 1206, 1187, 1092, 851, 757 cm-1; HRMS
(ESI) calculated [M + H]+ for C13H14NO: 215.1019; found: 215.1016.
mp: 56-58 ºC; 1H NMR (400 MHz, CDCl3): δ 1.40 (t, J=7.10 Hz 3H), 4.38
(q, J=7.02 Hz 2H), 7.44 - 7.63 (m 1H), 7.89 - 8.05 (2H), 8.25 (s 3H ). 13
C
NMR (101 MHz, CDCl3): δ 14.7, 62.6,102.9, 115.1, 129.1, 130.9, 131.3 ,
133.2,154.9, 162.3; IR Vmax = 2983, 2224, 1718, 1605, 1285, 1201, 1089,
1012, 767,685, cm-1; HRMS (ESI) calculated [M + H]+ for C12H12NO2:
202.0863; found: 202.0860.
Ethyl (E)-2-cyano-3-(4-nitrophenyl)acrylate(3zh):
White solid; (Pet. ether /EtOAc = 90/10); Yield: 120mg, 74%; Yellow
solid; mp: 166-168 ºC; 1H NMR (400 MHz, CDCl3): δ 1.36 (t, J=7.14 Hz,
3H), 4.33 (q, J=6.76 Hz, 2H), 6.95 (d, J=8.27 Hz, 2H), 7.95 (d, J=9.02 Hz,
2H), 8.12 (s, 1H). 13C NMR (101 MHz, CDCl3): δ 14.0, 55.45,62.2, 76.6,
Ethyl (E)-2-cyano-3-(naphthalen-1-yl)acrylate(3zb):
White solid; (Pet. ether /EtOAc = 90/10); Yield: 126 mg, 81%; Yellow
solid; mp: 80-82 ºC; 1H NMR (400 MHz, CDCl3): δ 1.44 (t, J=7.14 Hz, 3H),
4.44 (q, J=6.77 Hz, 2H), 7.48 - 7.70 (m, 3H), 7.89 (d, J=7.52 Hz, 1H),
8.00 (t, J=7.52 Hz, 2H), 8.30 (d, J =7.52 Hz, 1H), 9.08 (s, 1H). 13C NMR
(101 MHz, CDCl3): δ 14.0, 62.6, 105.5, 115.2, 122.6, 125.1, 126.6, 127.6,
128.0, 128.0 ,128.9, 131.4, 133.2, 133.2, 152.4, 162.1; IR Vmax = 2983,
2225, 1724, 1601, 1278, 1238,1080,781,760, cm-1; HRMS (ESI)
calculated [M+H]+ for C16H14NO2: 252.1019; found: 252.1015.
77.3, 99.1, 114.5, 116.0, 124.1, 133.4, 154.1, 162.8, 163.6; IR Vmax
=
2924, 2226, 1720, 1515, 1347, 1286, 858, 765, 666cm-1; HRMS (ESI)
calculated [M + H]+ for C12H11N2O4: 247.0713; found: 247.0686.
Ethyl (E)-2-cyano-3-(furan-2-yl)acrylate(3zi):
White solid; (Pet. ether /EtOAc = 90/10); Yield: 153 mg, 78%; Yellow
solid; mp: 88-90 ºC; 1H NMR (200 MHz, CDCl3): δ 1.39 (t, J=7.14 Hz, 3H),
4.36 (q, J=7.07 Hz, 2H), 6.67 (dd, J=3.54, 1.64 Hz, 1H), 7.40 (d, J=3.66
Hz, 1H), 7.76 (d, J=1.39 Hz, 1H), 8.02 (s, 1H). 13C NMR (50 MHz,
CDCl3): δ 14.1, 62.5, 98.6,113.7, 115.2, 121.6, 139.3,148.2, 148.6,
162.5; IR Vmax = 3040, 2926, 2224, 1716, 1621, 1262, 1212, 1025, 761
cm-1; HRMS (ESI) calculated [M + H]+ for C10H10NO3: 192.0655; found:
192.0553.
Ethyl(E)-2-cyano-3-(2-methoxyphenyl)acrylate(3zc)
White solid; (Pet. ether /EtOAc = 90/10); Yield: 128 mg, 76%; Yellow
solid; mp: 72 ºC; 1H NMR (200 MHz, CDCl3): δ 1.39 (t, J=7.14 Hz 3H),
3.90 (s 3H), 4.37 (q, J=7.07 Hz 2H), 6.87 - 7.15 (m 2H), 7.51 (ddd,
J=8.53, 7.26, 1.64 Hz 1H), 8.28 (dd, J=7.89, 1.58 Hz 1H), 8.75 (s 1H );
13C NMR (50 MHz, CDCl3): δ 14.0, 55.6, 62.3, 102.2, 111.0, 115.7,
120.6, 120.8, 129.2, 134.8, 149.6, 159.1, 162.6 ; IR Vmax = 2984, 2222,
1716, 1593, 1466, 1368, 1241, 1164, 751, cm-1; HRMS (ESI) calculated
[M + H]+ for C13H14NO3: 232.0968; found: 232.0964.
2-(diphenylmethylene)malononitrile(3zj):
White solid; (Pet. Ether/EtOAc = 85/15); Yield: 106 mg, 84% ; 1H NMR
(400 MHz, CDCl3): δ 7.41 - 7.55 (m, 8H), 7.57 - 7.62 (m, 2H). 13C NMR
(101 MHz, CDCl3): δ 76.6, 77.3 , 81.65, 113.86, 128.8, 130.4, 132.6,
136.0, 174.9; IR Vmax = 2361, 2223, 1531, 702 cm-1; HRMS (ESI)
calculated [M + H]+ for C16H11N2: 231.0917; found: 231.0919.
Ethyl (E)-2-cyano-3-(o-tolyl)acrylate(3zd):
White solid; (Pet. ether /EtOAc = 90/10); Yield: 148 mg, 84%; Yellow
solid; mp: 55-57 ºC ; 1H NMR (200 MHz, CDCl3): δ 1.41 (t, J=7.14 Hz,
3H), 2.46 (s, 3H), 4.40 (q, J=7.07 Hz, 2H), 7.21 - 7.49 (m, 3H,) 7.96 -
8.24 (m, 1H), 8.58 (s, 1H). 13C NMR (50 MHz, CDCl3): δ 14.0, 19.7, 62.6,
104.46, 115., 126.6, 128.5, 130.5, 130.92, 132.6, 139.6, 153.27, 162.3;
IR Vmax = 2995, 2218, 1724, 1600, 1269, 1208, 1192, 1094, 818, 762cm-
1; HRMS (ESI) calculated [M + H]+ for C13H14NO2: 216.1019; found:
215.1016.
Acknowledgments
B.D.R thankful to UGC-New Delhi for the award of Fellowship.
Keywords:: (Diacetoxyiodo)benzene; oxidative olefination;
amines; cyanoacrylamide.
Ethyl (E)-3-(2-chlorophenyl)-2-cyanoacrylate(3ze):
[1] a) D. Michaud, F. T. Boullet, J. Hamelin, Tetrahedron Lett. 1997, 32, 7563-
White solid; (Pet. ether /EtOAc = 90/10); Yield: 133 mg, 80%; Yellow
solid; mp: 50-52 ºC; 1H NMR (400 MHz, CDCl3): δ 1.29 - 1.34 (m, 3H),
4.30 (q, J=6.87 Hz, 2H), 7.27 - 7.32 (m, 1H) 7.36 - 7.39 (m, 2H), 8.12 (d,
J=7.63 Hz, 1H), 8.54 (s, 1H). 13C NMR (101 MHz, CDCl3): δ 13.7, 62.5,
105.7, 114.3, 127.08.0, 129.36, 129.9, 133.3,135.9, 150.3, 161.2; IR Vmax
= 2981, 2226, 1728, 1605, 1280, 1213, , 818, 762 cm-1; HRMS (ESI)
calculated [M + H]+ for C12H11ClNO2: 236.0473; found: 236.0469.
7564; b) J. G. Shim, J. C. Park, C. S. Cho, S. C. Shim, Y. Yamamoto,
Chem. Commun. 2002, 0, 852–853; c) M. C. Kloetzel, The Diels–Alder
Reaction with Maleic Anhydride. Organic Reactions. 1948, 4, 1-59; d) H.
Moison, F.T. Boullet, A. Foucaud, Tetrahedron, 1987, 43, 537-542; e) R.
Kumbhare, M. Sridhar, Catal. Commun. 2008, 9, 403-405; f) D. Xue, Y.C.
Chen, X. Cui, Q. W. Wang, J. Zhu, J. G. Deng, J. Org. Chem. 2005, 70,
3584-3591; g) Q. He, Z. Xu, D. Jiang, W. Ai, R. Shi, S Qian, Z. Wang,
RSC Adv. 2014, 4, 8671-8674; h) S. R. Pollack, J. T. Kuethe, Org. Lett.
2016, 18, 6388-6391; i) S. meninno, L. Zullo J. Overguaard, A. Lattanzi,
Adv.Synth,Catal. 2017, 359, 913-918. j) J. H. Barber, K. P. Spina,
Tetrahedron Lett. 24, 1983, 36, 3835-3838; k) S. K. Rai, S. Khanam, R. S.
Khanna, A. K. Tewari, RSC Adv. 2014, 4, 44141-44145; l) X. Z. Fan, J. W.
Rong, H. L. Wu, Q. Zhou, H. P. Deng, J. D. Tan, C. W. Xue, L. Z. Wu, H.
R. Tao, J. Wu. Angew. Chem. Int. Ed. 2018, 57, 8514 -8518.
Ethyl (E)-2-cyano-3-(4-methoxyphenyl)acrylate(3zf)
White solid; (Pet. ether /EtOAc = 90/10); Yield: 144 mg, 86%; Yellow
solid; mp: 78-80 ºC; 1H NMR (400 MHz, CDCl3): δ 1.36 (t, J=7.14 Hz,
3H), 3.85 (s, 3H), 4.33 (q, J=6.76 Hz, 2H), 6.95 (d, J=8.27 Hz, 2H), 7.95
(d, J=9.02 Hz, 2H) 8.12 (s, 1H). 13C NMR (101 MHz, CDCl3): δ 14.2 ,
55.4, 62.2, 99.1, 114.5, 116.0, 124.1, 133.4, 154.1, 162.8, 163.6; IR Vmax
= 2982, 2220, 1716, 1585, 1511, 1427, 1257, 1171, 1018, 834, 761, cm-
1; HRMS (ESI) calculated [M + H]+ for C13H14NO3: 232.0968; found:
232.0964.
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Hypervalent
mediated
iodine
oxidative
Oxidative Olefination
Bapurao. D. Rupanawarab Sruthi M.
olefination of amines with
an active methylene
compound for the
formation of electrophilic
alkenes under mild
V.c and Gurunath Suryavanshi ab
*
Page No. – Page No.
reaction conditions in good
to excellent yields.
Hypervalent Iodine(III)Mediated
Oxidative Olefination of
Benzylamine with an Active
Methylene Compound
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