MMZNiY-Catalyzed Tsuji–Trost Type of Reaction: A Selective Mono/Bis Allylation of Dicarbonyl Compounds

Article abstract of DOI:10.1007/s10562-017-2185-3

Abstract: An alternative method to Pd-catalyzed Tsuji–Trost reaction is developed and it provides a simpler route for the selective synthesis of a broad range of mono-/bis-allylated and cinnamylated 1,3-dicarbonyl compounds using MMZ_NiY catalyst at room temperature. Product selectivity can be controlled by the proper choice of catalyst. The catalyst was also well characterized by SEM, TEM, HRTEM, EDAX and X-ray analysis. Other advantages of catalyst like its ease of preparation, functional tolerance and its reusability are also highlighted.

Full text of DOI:10.1007/s10562-017-2185-3

Catal Lett
DOI 10.1007/s10562-017-2185-3
MMZNiY-Catalyzed Tsuji–Trost Type of Reaction: A Selective
Mono/Bis Allylation of Dicarbonyl Compounds
Samuthirarajan Senthilkumar1 · Cheirmakani Thangapriya1 ·
Raman Alagumurugayee1 · Mayilvasagam Kumarraja1
Received: 20 June 2017 / Accepted: 25 August 2017
© Springer Science+Business Media, LLC 2017
Abstract An alternative method to Pd-catalyzed Tsuji–
Trost reaction is developed and it provides a simpler route
for the selective synthesis of a broad range of mono-/bis-
allylated and cinnamylated 1,3-dicarbonyl compounds using
MMZNiY catalyst at room temperature. Product selectivity
can be controlled by the proper choice of catalyst. The cata-
lyst was also well characterized by SEM, TEM, HRTEM,
EDAX and X-ray analysis. Other advantages of catalyst like
its ease of preparation, functional tolerance and its reusabil-
ity are also highlighted.
1 Introduction
Allylation of carbonyl compounds has been proved as a
valuable tool for carbon chain elongation and thus exten-
sively used for the functionalization of biologically active
compounds which find pharmaceutical applications such as
antibiotic, anticancer, DNA polymerase and HIV reverse
transcriptase inhibitors [1–7]. Generally, Pd and its deriva-
tives have been used to catalyze the allylic substitution at
active methylenic compounds and these reactions are called
as Tsuji–Trost reactions [8–18]. A few other metal com-
plexes like Ru [19, 20], Ir [21, 22], Mo [23], W [24–26],
Ce [27], Co [28, 29] and Bi [30] were also reported to cata-
lyze the allylic substitution reactions. However, most of the
described procedures suffer from the disadvantages such as
the use of expensive metals, need of external ligands, tedious
workup, longer reaction time, mixture of products and func-
tional intolerance. As a consequence, development of new
methods or materials to overcome these limitations is still
in demand to make the procedure convenient and simple.
In recent years, the research activity for developing nano-
materials has grown exponentially owing to the fact that they
offer better solutions to the challenges faced by various field.
Niasari et al. have reported the preparation of various nano-
materials and investigated their catalytic properties [31–37].
Indeed, hierarchical nanoporous materials find many poten-
tial applications in the fields of drug delivery, hydrocarbon
cracking, product selectivity [38–40] etc. In continuation of
our interest in showing the multiple catalytic applications of
hierarchically architectured MMZY in organic transforma-
tions [41, 42], herein we report the selective allylation and
cinnamylation of 1,3-dicarbonyl compounds.
Graphical Abstract
R3
O
R3 R3
O
O
MMZNiY, K2CO3
ACN, rt
O
R3
Br
O
O
+
or
R2
R1
R2
R1
R2
R1
2
1
3
4
R1= CH3, C6H5, OC2H5
R2 = OC2H5, OCH3, CH3, C6H5, OC2H5
R3= H, C6H5
Keywords Ni-catalyzed Tsuji–Trost reaction ·
1,3-Dicarbonyl compounds · Allylation · Cinnamylation ·
MMZNi-Y zeolite
Electronic supplementary material The online version
of this article (doi:10.1007/s10562-017-2185-3) contains
supplementary material, which is available to authorized users.
* Mayilvasagam Kumarraja
dr.kumarraja@gmail.com
1
Centre for Research and Post-graduate Studies in Chemistry,
Ayya Nadar Janaki Ammal College (Autonomous), Sivakasi,
Tamil Nadu 626 124, India
Vol.:(0123456789)
1 3

S. Senthilkumar et al.
exclusively (entry 9). We have also examined the recycling
of MMZNiY to see its efficiency which afforded the same
yield even after two time usage.
2 Results and Discussion
We have focused our initial studies on the optimization
of reaction conditions and screening of suitable catalyst
for the allylation of methylacetoacetate and the interest-
ing results are summarized in Table 1. As there was no
reaction in the absence of catalyst, different metal ion-
exchanged zeolites were employed to find out the efficient
catalyst for the present investigation. Bronsted acidic
types of zeolites like HY and CaY produced a mixture of
allylated products with very poor yields (Table 1, entries
2 and 7).
The structural morphology of the hierarchical nano-
porous MMZNiY zeolite was characterized by SEM, TEM,
HRTEM, EDAX and powder-XRD methods (Figs. 1, 2).
It clearly shows the uniform formation of Ni(II) species in
the MMZY framework of the catalyst with the particle size
range of 0.5–1 μm. The XRD pattern of the MMZNiY are
also found to be in good agreement with the parent zeolite
framework structure. It clearly reveals that there is no change
in crystallinity.
MMZNiY also shows its excellent tolerance toward the
sterically crowded cinnamylation and the efficiency in selec-
tivity toward mono-/bis-cinnamylated products (77–89%,
Table 2).
In the presence of alkali ion-exchanged zeolites also,
we obtained a poor yield without significant selectivity
(entries 3 and 8). However, in the presence of transi-
tion metal ions exchanged zeolite like CuII-Y, NiII-Y and
CoII-Y, the reaction proceeded faster and they piped out
the allylated product from moderate to excellent yields
(entries 4–6). Among them, Nickel-exchanged zeolite was
found to be a very efficient catalyst which afforded 83%
of mono-allylated product (entry 5). Our earlier reports on
the use of MMZY [41, 42] in other organic transformations
have prompted us to prepare NiII-exchanged MMZY and
employ in the present study. Surprisingly Ni-exchanged
MMZY catalyst produced 96% of monoallylated product
The difference in reactivity of allyl/cinnamyl bromide
with 1,3-dicarbonyl compounds is also attributed to the pka
value of the substrates catalyzed by MMZNiY. In the case
of keto-esters (Table 2, entries 1–8), mono-allylation is the
major product (77–96%) due to their pka value are greater
than 9, whereas in the case of diketones (entries 11–16),
bis-allylation dominates (80–94%) due to their pka value
are lesser than 9. However the exceptional case is dibenzoyl-
methane (entries 10 and 11), it results only a mono-allylation
Table 1 Screening of catalysts for the allylation of 1,3-dicarbonyl compounds
O
O
O
O
catalyst
rt, 6h
OCH3
+
Br
OCH3
O
O
+
OCH3
2a
1a
3a
4a
(mono)
(bis)
Entry
Catalyst
% Yielda
(3a) (mono)
(4a) (bis)
1
2
3
4
5
6
7
8
9
Neat
HY
–
–
19
21
61
83
70
24
19
96
14
18
29
11
22
19
06
–
NaY
CuY
NiY
CoY
CaY
CsY
MMZNiY
Reaction conditions: a mixture of methylacetoacetate (1 mmol), allyl bromide (2 mmol), catalyst (100 mg), K2CO3 (1 mmol) and acetonitrile
(3 ml) were stirred at room temperature for 6 h
aIsolated yields
1 3

MMZNiY-Catalyzed Tsuji–Trost Type of Reaction: A Selective Mono/Bis Allylation of Dicarbonyl…
Fig. 1 a SEM. b TEM. c EDAX and d p-XRD spectrum of MMZNiY zeolite
which is a contrary observation with respect to other dik-
etones employed in the present study. These interesting
results are attributed to the cavity size of MMZNiY. It is
worthy to note in the case of dibenzoylmethane where the
nanocavities inside the MMZNiY arrests the free mobility
of bulkier substrates and thus allows only mono-allylation/
cinnamylation.
oxidative addition, the leaving group bromide is expelled
and it gives η2Ӆ-allyl complex. Nucleophilic carbon then
attacks the metal centre followed by a reductive elimination
gives selectively allylated/cinnamylated product.
A careful study on the comparison of data with other
reported catalysts has been made and the parameters are pre-
sented in Table 3. It clearly reveals that our catalytic system
shows excellent selectivity with higher yields and moreo-
ver it is reusable when compared to other catalysts which
requires the addition of pyridine, aryl phosphate ligand
and argon atmosphere, reflux conditions, longer reaction
time etc. It also includes other side reactions like dehydra-
tion, cyclization, mixture of products and failure to achieve
cinnamylation.
The role of MMZNiY in the allylation/cinnamylation can
be easily understood through the proposed mechanism [18]
that easy removal of acidic methylenic hydrogens of dicar-
bonyls by a simple base produces the nucleophilic methine
carbon. At the same time, MMZNiY acts as a Lewis acid [39]
and therefore it can readily coordinate with the double bond
of allyl group and forms a Ӆ-Ni-allyl complex. During the
1 3

S. Senthilkumar et al.
Fig. 2 HRTEM images of MMZNiY shows the presence of Ni ions within the cages and on the external surface of zeolite framework
3 Conclusions
4 Experimental Methods
In conclusion, we have developed a simple procedure for the
selective mono/bis allylation and cinnamylation of various
dicarbonyl compounds promoted by an inexpensive, reus-
able, non-toxic and environmentally benign novel solid acid
MMZNiY catalyst. These reactions encompass a broad range
of 1,3-dicarbonyls as well as simple and bulkier allylating
agents. The other advantages of this procedure are no need
of external ligands, use of a simple base, shorter reaction
time and excellent selectivity with higher yields.
4.1 Synthesis of MMZNiY using Nanoporous Zeolite Y
(MMZY)
The nanoporous MMZY zeolite was synthesized from
the commercially available NaY zeolite according to the
reported procedure [43, 44]. The as prepared MMZY was
stirred with nickel nitrate (100 ml, 10%) solution at 70 °C
for 12 h. The exchange was repeated at least three times.
Each time after exchange, the zeolite powder was washed
1 3

MMZNiY-Catalyzed Tsuji–Trost Type of Reaction: A Selective Mono/Bis Allylation of Dicarbonyl…
Yield[a] (%)
Mono Bis
Table 2 Allylation and
cinnamylation of various
1,3-dicarbonyl compounds
using MMZNiY zeolite
Allylating
agent
Substrate
(1)
S.No
Major Product
(2)
(3)
(4)
O
O
1.
O
O
O
92
--
Br
O
(1a)
(3a)
O
O
Br
O
O
O
2.
90
--
O
(1a)
(3b)
O
O
O
O
O
Br
3.
4.
96
87
--
--
O
(1b)
(3c)
O
O
O
O
Br
O
O
(1b)
(3d)
O
O
O
O
O
Br
5.
6.
89
81
--
--
O
(1c)
(3e)
O
O
O
O
Br
O
O
(3f)
(1c)
COOC2H5
COOC2H5
Br
7.
8.
93
89
--
--
COOC2H5
COOC2H5
(3g)
(1d)
COOC2H5
Br
COOC2H5
COOC2H5
COOC2H5
(1d)
(3h)
1 3

S. Senthilkumar et al.
Yield[a] (%)
Mono Bis
Table 2 (continued)
Allylating
agent
Substrate
(1)
S.No
Major Product
(2)
(3)
(4)
O
O
O
O
Br
9.
85
--
(1e)
(3i)
O
O
O
O
10.
Br
77
-
(3j)
(1e)
O
O
O
Br
11.
12.
--
--
92
87
O
(1f)
(1f)
(4k)
O
O
Br
O
O
(4l)
Br
13.
14.
O
O
--
94
86
O
O
(4m)
(1g)
O
--
O
Br
O
O
(1g)
(1h)
(4n)
(4o)
15.
16.
--
--
92
80
Br
O
O
O
O
Br
O
O
O
O
(1h)
(4p)
Reaction conditions: a mixture of 1,3-dicarbonyl (1 mmol), allyl bromide (2 mmol),
K2CO3 (1 mmol), MMZNi-Y (100 mg) and solvent (3 ml) were stirred at room temperature
for 6 h
aIsolated yield
1 3

MMZNiY-Catalyzed Tsuji–Trost Type of Reaction: A Selective Mono/Bis Allylation of Dicarbonyl…
Table 3 A Comparative study
S.No. Catalyst
References Solvent
Temp.
50 °C
Time (h)
Yield (%)
with other reported catalytic
systems for the allylation of
1,3-dicarbonyl compounds
1
2
3
4
5
6
7
8
Pd(π-allyl)/DPCB
[9]
Pyridine
Toluene (Ar atm.) 80 °C
H2O/AcOEt
THF/H2O
CH3CN
3–12
2–25
13–21
6–12
16 h–2 days >80
4
>85
>80
>70
80–90
Pd{P(OC6H5)3}4
PdCl(ƞ3-C3H5)/tppts
PdCl2, TBAB
Ru(Cp) (MeCN)3[PF6] [20]
CTAN
CoCl2
[11]
[14]
[15]
rt
Reflux
40 °C
rt
70 °C
100 °C
[27]
[29]
[30]
CH3CN, Et3N
DCE
CH3NO2
60–80
30–67
58–96
8–12
6
Bi(OTf)3
repeatedly with distilled water and then dried and activated
at 450 °C before use.
4.3 Spectral Data of the Isolated Products
Transmission Electron Microscopy (TEM) image of
MMZNiY was obtained using a JEOL JEM-2100 LaB6
instrument equipped with the high-resolution (HRP),
style objective-lens pole piece at an acceleration voltage
of 200 kV. Scanning Electron Microscopy (SEM) images
were taken by using FEI Quanta FEG 200-High Resolu-
tion Scanning Electron Microscope. HR-TEM images
were recorded in JEOL—JEM-2100, at operating voltage
of 200 kV with Lanthanumhexaborate filament using fer-
mionic gun. The X–ray diffraction (XRD) patterns were
taken with a Bruker D8 advance, Cu Kα radiation (40 kV,
30 mA). EDAX analysis was carriedout using Bruker
instrument.
4.3.1 Ethyl-2-acetyl-pent-4-enoate (3a)
Colorless Oil, 1H NMR (300 MHz, CDCl3): δ (5.72–5.63,
m, 1H), (5.06–4.96, dd, 2H), (4.16–4.09, q, 2H), (3.46, t,
1H), (2.52, t, 2H), (2.17, s, 3H), (1.24, t, 3H). 13C NMR
(75 MHz, CDCl3): δ 202.30, 169.0, 133.95, 117.20, 61.19,
58.96, 31.91, 28.87, 13.84.
4.3.2 Ethyl-2-acetyl-5-phenyl pent-4-enoate (3b)
Colorless Oil, 1H NMR (300 MHz, CDCl3): δ (7.31–7.29, m,
4H), (7.22, m, 1H), (6.45, d, 1H), (6.17–6.03, m, 1H), (4.21,
q, 2H), (3.59, t, 1H), (2.77, m, 2H), (2.26, s, 3H),(1.25, t,
3H), 13C NMR (75 MHz, CDCl3): δ 168.95, 136.83, 133.89,
132.51, 128.25, 127.13, 125.97, 125.92, 125.52, 123.61,
61.18, 59.40, 35.63, 31.26, 28.86, 13.85.
4.2 General Procedure for the Allylation/
Cinnamylation of 1,3-Dicarbonyl Compounds
Using MMZNiY Zeolite
4.3.3 Methyl-2-acetyl pent-4-enoate (3c)
A mixture of 1,3-dicarbonyls (1 mmol), allyl/cinnamyl bro-
mide (2 mmol) and K2CO3 (1 mmol) were added to the reac-
tion tube, which contains acetonitrile (3 ml) and 100 mg
of freshly activated MMZNiY zeolite. The reaction mixture
was stirred for 6 h. Products were extracted from the reac-
tion mixture after the addition of 15 ml of dichloromethane
solvent and allowed for 2 h stirring again. The catalyst was
separated from the reaction mixture by simple filtration.
Then, the solvents were removed by evaporation in a rotary
evaporator. Proceedings of the reaction was constantly moni-
tored by TLC [silica gel, pet ether:ethyl acetate (8:2)]. The
products were purified by column Chromatography [using
pet ether (97%):ethyl acetate (3%)].
Colorless Oil, H NMR (300 MHz, CDCl3): δ (5.81–5.67, m,
1H) (5.12, d, 1H), (5.03, d, 1H), (3.74, s, 3H), (3.55, t, 1H),
(2.61, t, 2H), (2.24, s, 3H).
4.3.4 Methyl-2-acetyl-5-phenyl pent-4-enoate (3d)
Yellow Oil, 1H NMR (300 MHz, CDCl3): δ (7.35–7.3, m,
4H), (7.22–7.25, m, 1H), (6.47, d, 1H), (5.96–6.17, m, 1H),
(3.75, s, 3H), (3.49, t, 1H), (2.71–2.46, m, 2H), (2.09, s, 3H).
4.3.5 Ethyl-2-benzoyl-pent-4-enoate (3e)
1
Brown Oil, H NMR (300 MHz, CDCl3): δ (8.01, d, 2H),
All the isolated mono- and bis-allylated/cinnamylated car-
(7.61, t, 1H), (7.48, t, 2H), (5.86–5.77, m, 1H), (5.15–5.02,
dd, 2H), (4.4, t, 1H), (4.14, q, 2H), (2.78–2.72, m, 2H),
(1.17, t, 3H), 13C NMR(75 MHz, CDCl3): δ 0.194.50,
169.37, 136.15, 134.47, 133.52, 128.71, 128.60, 117.40,
61.44, 53.91, 32.97, 13.99. GC-MS: Calcd. for C14H16O3:
232.10. Found 232.1.
bonyl compounds were characterized by 1H NMR and 13
C
NMR spectra, were obtained on Bruker NMR (300 MHz)
instrument in CDCl3. GC-MS spectrum was recorded
on Agilent-7820A GC system with 5977E MSD (DB-5
Column).
1 3

S. Senthilkumar et al.
4.3.6 Ethyl-2-benzoyl-5-phenyl-pent-4-enoate (3f)
4.3.14 2,2-Dicinnamyl cyclohexane-1,3-dione (4n)
1
Yellow Oil, 1H NMR (300 MHz, CDCl3): δ (8.03, d, 2H),
(7.61–7.49, m, 3H), (7.31–7.27, m, 4H), (7.22–7.21, m, 1H),
(6.49, d, 1H), (6.26–6.16, dt, 1H), (4.47, t, 1H) (4.16, q, 2H),
(2.93, m, 2H), (1.18, s, 3H).
Yellow Solid, mp 134–136 °C, H NMR (300 MHz,
CDCl3): δ (7.28–7.25, m, 8H), (7.23–7.19, m, 2H), (6.38,
d, 2H), (5.99–5.93, m, 2H), (2.71, d, 4H), (2.54, t, 4H),
(1.86, m, 2H).
4.3.7 Diethyl-2-allylmalonate (3g)
4.3.15 2,2-Diallyl-5,5-dimethyl cyclohexane-1,3-dione
(4o)
Yellow Oil, 1H NMR (300 MHz, CDCl3): δ (5.8–5.71, m,
1H), (5.03, d, 1H), (4.97, d, 1H), (4. 12, q, 4H), (3.19, t, 1H),
(2.7, d, 2H), (1.3, t, 6H).
1
Colorless Oil, H NMR (300 MHz, CDCl3): δ (5.65–5.5,
m, 2H), (5.1–5.03, dd, 4H), (2.59, s, 4H), (2.51, d, 4H),
(0.96, s, 6H). 13C NMR (75 MHz, CDCl3): δ 208.45,
132.33, 119.29, 67.80, 51.88, 38.66, 30.59, 29.52.
4.3.8 Diethyl-2-cinnamyl malonate (3h)
Colorless Oil, 1H NMR (300 MHz, CDCl3): δ (7.32–7.25,
m, 4H), (7.22 7.20, m, 1H), (6.48, d, 1H), (6.18–6.14, m,
1H), (4.23–4.17, m, 4H), (3.49, t, 1H), (2.87–2.78, m, 2H),
(1.25, t, 6H).
4.3.16 2,2-Dicinnamyl-5,5-dimethylcyclohexane-1,3-dione
(4p)
1
Pale Yellow Solid, mp 149–150 °C, H NMR (300 MHz,
4.3.9 2-Allyl-1,3-diphenyl propane-1,3-dione (3i)
CDCl3): δ (7.30–7.25, m, 8H), (7.21–7.18, m, 2H), (6.42,
d, 2H), (6.03–5.97, m, 2H), (2.69, d, 4H), (2.57, s, 4H),
(0.94, s, 6H).
1
White Solid, mp 94–97 °C, H NMR (300 MHz, CDCl3):
δ (7.95, d, 4H), (7.56, t, 2H), (7.43, t, 4H), (5.91–5.83, m,
1H), (5.30, t, 1H), (5.10, d, 1H), (5.02, d, 1H), (2.9, t, 2H).
Acknowledgements Authors thank The Principal and The Man-
agement of ANJA College, Sivakasi for providing necessary facili-
ties as well as the University Grants Commission, New Delhi [F. No.
41-334/2012 (SR)] for its financial support.
4.3.10 2-Cinnamyl-1,3-diphenyl propane-1,3-dione (3j)
1
Pale yellow solid, mp 118–120 °C, H NMR (300 MHz,
CDCl3): δ (7.97, d, 4H), (7.56, t, 2H), (7.44, t, 4H), (7.24, d,
4H), (7.18, m, 1H), (6.46, d, 1H), (6.27–6.21, m, 1H), (5.35,
t, 1H), (3.02, t, 2H).
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MMZNiY-Catalyzed Tsuji–Trost Type of Reaction: A Selective Mono/Bis Allylation of Dicarbonyl…
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