Synthesis of internal olefins by direct coupling of alcohols and olefins over MoΒ zeolite

Article abstract of DOI:10.1016/j.catcom.2019.01.027

An efficient and novel Moβ zeolite catalyzed sp²-sp³ C–C bond development reaction over the direct coupling of alcohols and alkenes has been performed in solvent free environment. The current method gives an attractive access to a wide variety of polysubstituted alkenes in good to excellent yields. The Moβ zeolite was effectively reused for up to 5 successive cycles.

Full text of DOI:10.1016/j.catcom.2019.01.027

Accepted Manuscript
Synthesis of internal olefins by direct coupling of alcohols and
olefins over Moβ zeolite
Chevella Durgaiah, Macharla Arun Kumar, Kodumuri Srujana,
Banothu Rammurthy, Gajula Krishna Sai, Amrutham Vasu,
Gennadievna Grigor'eva Nellya, Nama Narender
PII:
S1566-7367(19)30028-7
DOI:
Reference:
https://doi.org/10.1016/j.catcom.2019.01.027
CATCOM 5611
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
1 November 2018
28 January 2019
30 January 2019
Please cite this article as: C. Durgaiah, M.A. Kumar, K. Srujana, et al., Synthesis of
internal olefins by direct coupling of alcohols and olefins over Moβ zeolite, Catalysis
Communications, https://doi.org/10.1016/j.catcom.2019.01.027
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ACCEPTED MANUSCRIPT
Synthesis of Internal Olefins by Direct Coupling of Alcohols and Olefins over
Moβ Zeolite†
Chevella Durgaiaha, Macharla Arun Kumara, Kodumuri Srujanaa, Banothu Rammurthya,b, Gajula
Krishna Saia,b, Amrutham Vasua,b, Gennadievna Grigor’eva Nellyac, Nama Narendera,b*
a C&FC Division, CSIR-Indian Institute of Chemical Technology, Hyderabad, Telangana, India-500 007.
b Academy of Scientific and Innovative Research
c IPC RAS, 141 prosp, Oktyabrya, 450075 Ufa, Russian Federation
* Corresponding author E-Mail: narendern33@yahoo.co.in, nama.iict@gov.in
Tel.: +91–40-27191703; Fax: +91-40-27160387/27160757
† IICT-Manuscript communication number: IICT/Pubs./2018/335

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Abstract
An efficient and novel Moβ zeolite catalyzed sp2-sp3 C-C bond development reaction over
the direct coupling of alcohols and alkenes has been performed in solvent free environment. The
current method gives an attractive access to a wide variety of polysubstituted alkenes in good to
excellent yields. The Moβ zeolite was effectively reused for up to 5 successive cycles.
Keywords: Alkenes, Alcohols, Cross-Coupling, Internal alkenes, Zeolites
1. Introduction
The development of C(sp2)-C(sp3) bond-construction reaction is one of the vital reactions
in modern synthetic organic chemistry [1]. Traditionally, various protocols for the construction
of sp2-sp3 C-C bonds were developed with various coupling reactions such as Heck, Stille,
Hiyama and Negishi coupling [2-7]. However, the requirement of additional synthesis steps for
the effective precursors, use of expensive/toxic homogenous catalysts, formation of
stoichiometric amounts of wastes, requirement for functionalized starting materials make such a
method justly unattractive. Hence, there is a solid requirement for establishing methodologies for
the construction of sp2-sp3 C-C bonds which includes the straight coupling of alcohols and
olefins due to its environmentally friendly and atom-efficient nature because only water is
produced as a side product [8-10]. Currently, very few protocols for the straight coupling of
alcohols and alkenes to develop sp2-sp3 C-C bonds were reported [11-20]. However, most of
these protocols have one or more drawbacks like use of expensive Pd catalysts [11,12], toxic
halogenated solvents like 1,2-dibromoethane, dichloromethane, and dichloroethane [13-16,18,
20] and homogeneous catalysts [17]. Therefore, there is a solid need for advancement of
polysubstituted olefins from alkenes with alcohols using heterogeneous catalysts under solvent

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free environment where the catalyst possibly simply recoverable and reused with no significant
damage in their catalytic activity.
In the past decade, solvent-free synthesis is an important part of green chemistry because
of its distinct advantages such as eliminates the use of toxic organic solvents, reduces pollution
and costs, requires less energy, faster reaction rates, reduction in reactor size, simplicity in
process and handling, which are especially important in industry [21-22].
Zeolites are crystalline microporous aluminosilicates with pore structures consisting of a
three dimensional (3D) network of SiO4 and AlO4 tetrahedra linked by corners sharing oxygen
ions [23]. Catalysts supported by different zeolites have played a significant role in both fine
chemical and petroleum industries because of their exclusive physical and chemical properties,
like high internal surface area, uniform channel size, strong acidity and good
thermal/hydrothermal stability, and unique molecular shape selectivity [24-25]. Among various
types of zeolites, Beta (β) has shown a flexible catalytic material for various applications in
industry [26]. Zeolite β exists of an intergrowth of two or more polymorphs comprised of a 3D
system of 12-membered ring channels with pore diameters of 0.55 × 0.55 nm and 0.76 × 0.64 nm
[27]. In recent years, catalysis supported by metal modified zeolite β attracted much attention
due to the large-pore channel system, large available micro-pore volume, eco-friendly nature,
high surface area, chemical and thermal stability, and the existence of active sites in various
concentrations which are helpful in a variety of acid-catalyzed reactions [28-34].
In extension of our interest towards the expansion of new and efficient synthetic methods
using zeolites [35-37], herein we wish to account the first example of zeolite catalyzed highly
regio- and stereoselective dehydrative cross-coupling of olefins with alcohols in solvent free
conditions, where water is the single by-product (Scheme 1). The definite goals of this protocol

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are to 1) determine the best zeolite and metal modified zeolite catalyst for the coupling reaction,
2) evaluate the effect of amount of catalyst, reaction temperature, reaction time, and mole ratio of
alkene to alcohol on the yield of coupling product, 3) check the possibility and limitations of the
reaction with different olefins and alcohols, 4) determine significant reaction route that leads to
coupling products, and 5) estimate the stability of catalyst over 5 cycles.
Scheme 1. Synthesis of Internal Alkenes.
2. Experimental Section
2.1. Synthesis of 10%Moβ zeolite
The zeolite NH4β was calcined at 500oC for 10 h to acquire zeolite HBeta (Hβ). Moβ was
synthesized using the modified impregnation method. Zeolite Hβ (2g) was added to the aqueous
solution of Mo precursor (368.05 mg of ammonium molybdate which contains 200 mg of Mo
was dissolved in 5 mL distilled water), then it was mixed homogenously with glass rod and was
o
placed on hot plate at 100 C to remove excess water for 1 h. After impregnation, the catalyst
o
o
was dried overnight at 100 C and calcined at 450 C for 6 h in the presence of static airflow
before using it for the reaction. The other metal modified zeolites (Snβ, Feβ, Coβ, Crβ, and Wβ)
were synthesized using same procedure stated above.
2.2. Experimental procedure
10% Moβ zeolite (100 mg) was introduced to the well stirred solution of vinylarene (1 mmol)
and alcohol (0.8 mmol) in a 15 mL of sealed vial and the reaction mixture was allowed to stir at
70 °C. After disappearance of the substrate (monitored by TLC) or after an appropriate time, the
reaction mixture was cooled to room temperature, diluted with ethyl acetate. The catalyst was
removed by filtration, rinsed with ethyl acetate and removal of solvent in vacuo yielded a crude

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residue. The crude residue was further purified by column chromatography on silica gel (230-
400 mesh) using ethyl acetate/hexane as eluent to afford pure products. All the products were
identified on the basis of NMR spectral data and quantified using gas chromatography. More
details on catalyst characterization and analytical procedures are provided in supporting
information.
3. Results and Discussion
3.1. Catalyst characterization
XRD studies revealed that no considerable modifications take place in the crystallinity of
the supported Hβ zeolite throughout the catalyst preparation process (Figures S1 and S2). The
outcome from FT-IR spectra of Hβ, and 10% Moβ zeolites indicate that Hβ was resistant
throughout the preparation of catalyst (Figure S3). The TEM image of 10% Moβ shows a
uniform and dense dispersion of the nano-sized particles of molybdenium oxide (2–8 nm) on the
surface of Hβ (Figure S4). The narrow scan of Mo(3d) on as-synthesized 10% Moβ shows
binding energy peaks at 233.37 and 236.64 eV, which are typical values of the 3d orbital doublet
of Mo6+ (Figure S5).
Temperature programmed desorption of ammonia (NH3-TPD) has been performed on the
zeolites and metal modified β zeolites to determine the strength and amount of acid sites (Table
Table 1 Acidity of Hβ and metal modified β zeolites
Catalyst
Aciditya
(mmol/g)
1.134
1.539
1.222
1.161
1.398
1.223
1.453
Acidic sites distributionb
LT-peakc MT-peakc HT-peakc
Hβ
42.9
47.9
33.5
35.1
30.8
34.3
34.1
40.7
45.0
42.1
35.9
35.5
52.2
51.1
65.7
36.3
43.9
39.7
15.0
16.2
31.0
12.7
18.1
-
29.6
15.4
15.3
10% Moβ
10% Snβ
10% Feβ
10% Wβ
10% Crβ
10% Coβ
2% Moβ
5% Moβ
1.167
1.288

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a
b
Total acidity amount determined by NH3-TPD. The NH3-TPD (%)
distribution of acidic sites. c LT-peak represents weak acid sites (150-250 C),
MT-peak represents medium acid sites (250-550 C) and HT-peak represents
strong acid sites (550- 650 C).
1, Table S2, Figure 1, Figure S6, and Figure S7). As can be seen in Table 1, the introduction of
metal cation on Hβ zeolite leads to increase in the amount of acid sites. Among the modified Hβ
zeolites, Moβ was found to have more number of acid sites present on the catalyst surface. As
the amount of Mo content increased from 2% to 10%, the amount of acid sites increased (Table
1, Figure S6).
Figure 1. NH3-TPD profile of a) Hβ, b) 10%Moβ, c) 10%Snβ, d) 10%Feβ, e) 10%Wβ, f) 10%Crβ, g) 10%Coβ.
3.2. Optimization of the reaction conditions
3.2.1. Effect of different catalysts on coupling reaction of styrene (1a) with benzhydrol (2a)
Initially, we investigated the direct cross-coupling reaction with styrene (1a) and
benzhydrol (2a) as the model substrates to optimize the various conditions of the reaction (Table
2 and S3). To select the foremost catalyst, initially the reaction was tested with montmorillonite

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K10, MCM-41, and various zeolites in sealed tube at 70 oC for 4 h (Table 2, entries 1-7). Besides
Montrimorillonite K10 and Hβ, other catalysts such as MCM-41, H-Mordenite, HZSM-5, HY,
and NaY did not or only sluggishly catalyzed the coupling reaction towards the corresponding
product 3a. Compared to the examined catalysts, Hβ exhibit the highest catalytic activity and
provided the corresponding coupling product in 67% yield because of large pore size and strong
acidic sites (Table 2, entry 7) [27]. No conversion was detected in the absence of catalyst (Table
2, entry 8).
The examination of various solvents with Hβ catalyst revealed that the performance of the
reaction in solvent free condition was considerably better compared to DCE, DCM, CHCl3,
toluene, H2O, and CH3CN (Table 2, entries 9-14). Later, we concentrated on gaining the highest
yield of 3a, and examined direct dehydrative cross-coupling of 1a with 2a using different metal
modified zeolite β catalysts (Table 2, entries 15-20). The results showed that the reaction with
Moβ zeolite exhibits best catalytic activity (gave the corresponding product in 83% yield and
87% selectivity) compared to other metal exchanged zeolite Hβ due to more number of acid sites
present on the catalyst surface (Table 2, entry 15). Results also showed that the order of
reactivity was Mo > Sn > Fe > Co > W > Cr. It is known that the modification of metal in
zeolites influences the strength of acid site, total acidity, and acid sites nature [37] (Table 1). As
can be seen from Table 1, the presence of more number of acid sites are responsible for the high
catalytic activity of 10% Moβ, where as other metal modified beta zeolites have less number of
acid sites which gave less catalytic activity. We had also investigated the cross-coupling of 1a
with 2a using Moβ catalyst with different Mo loadings (2, 5, 7, 10, and 12 wt%) (Table 2, entries
21-24). Yield of 3a was raised from 66 to 83 % with raise in Mo content from 2 to 10 wt%.
Whereas further increase in Mo loading did not show any considerable modification in the yield

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of 3a. This is due to the increase in the number of acid sites with raise in Mo content from 2 to
10 wt% (Table 2, Figure S6). The catalytic activity depends on many factors like amount of total
acid sites, surface area, pore size, and Si/Al ratio and it is difficult to clearly correlate all the
properties of the catalyst tested with the catalytic performance. The amount of total acid sites can
only be correlated to the catalytic activity in this study.
Table 2 Optimization of reaction conditionsa
Entry
1
Catalyst
HMCM-41
Montmorillonite K10
H-Mordenite
HZSM-5 (40)
HY
Solvent Yieldb (%)
-
-
-
4
38
6
2
3
4
5
-
0
-
4
6
NaY
-
0
7
8
9
Hβ
-
-
67
0
Without catalyst
Hβ
DCE
DCM
CHCl3
Toluene
H2O
CH3CN
61
44
21
14
<5
0
83
48
35
24
7
18
66
74
78
82
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Hβ
Hβ
Hβ
Hβ
Hβ
10% Moβ
10% Snβ
10% Feβ
10% Coβ
10% Crβ
10% Wβ
2% Moβ
5% Moβ
7% Moβ
12% Moβ
-
-
-
-
-
-
-
-
-
a Reaction conditions: 1a (1 mmol), 2a (0.8 mmol), catalyst (100
mg), solvent (2 mL), 70 °C, 4 h, sealed vial. Isolated yields
b
based on 2a.
3.2.2. Effect of amount of Moβ, temperature, reaction time and mole ratio on coupling reaction

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Once 10% Moβ was confirmed as the best catalyst for direct cross-coupling reaction of 1a
and 2a, the influence of amount of catalyst, reaction temperature, reaction time, and mole ratio of
1a and 2a were studied (Table S3). With increase in the amount of catalyst from 25 to 100 mg,
the yield of 3a was raised from 42 to 83%. Whereas, further increase in the amount of catalyst
from 100 to 125 mg has not shown any notable change in the yield of product 3a (Table S3,
entries 1-5). The same trend was observed with increase in reaction temperature and the reaction
time (Table S3, entries 6-12). The mole ratio of 1a to 2a also had a accountable influence on the
yield of 3a. While increase in the mole ratio of 1a to 2a (1:0.5 to 1:0.8), the yield of 3a was
increased from 73 to 83% (Table S3, entry 13 and 4). Whereas further increase in the mole ratio
of 1a to 2a (1:0.8 to 1:1 and 1:1.2), the yield of 3a was reduced from 83 to 71 and 68% due to
the formation of ether as a side product (Table S3, entries 14-15). From the above acquired data,
it can be confirmed that the optimized reaction parameters to obtain the best yield for this direct
o
cross-coupling reaction are 1:0.8 mole ratio of 1a to 2a at 70 C over 10% Moβ catalyst (100
mg).
3.3. Moβ catalyzed direct coupling reaction of 2a with various olefins
Based on the optimized parameters, the possibility and limitations for the reaction of
different olefins with 2a were examined (Table 3). Along with 1a, a set of substituted styrenes
consists of both electron-rich or electron-deficient groups were all appropriate reactants, and
produced the subsequent coupling products in excellent yields (Table 3, entries 1-11). The
sterically hindered disubstituted aromatic alkenes like prop-1-en-2-ylbenzene, 1-chloro-4-(prop-

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Table 3 Olefin variationa
Entry
1
Olefin
Product
Time (h) Yieldb (%)
4
83
1a
3a
2
3
4
5
3
3
3
3
86
85
88
78
1b
1c
1d
3b
3c
3d
1e
3e
6
7
4
4
4
6
6
78
78
80
70
76
1f
3f
1g
3g
3h
3i
8
1h
1i
9
10
1j
3j

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11
6
73
1k
1l
3k
12
13
12
2
00
89
3l
1m
3m
14
15
2
2
88
91
1n
3n
1o
3o
3p
16
17
18
3.5
3.5
6
90
87
85
1p
1q
3q
1r
1s
3r
3s
19
6
70
a
Reaction conditions: 1a-s (1 mmol), 2a (0.8 mmol), 10% Moβ (100 mg), 70 °C, sealed
vial. b Isolated yields based on 2a.
1-en-2-yl)benzene (1m and 1n) and ethene-1,1-diyldibenzene (1o) were also well tolerated in
this method, leading to the preferred products in excellent yields (Table 3, entries 13-15).
Additionally, cyclic internal olefins, such as indene (1p) and 1,2-dihydronaphthalene (1q) were
also exhibited excellent activities (Table 3, entries 16 and 17). Especially, due to the high steric
hindrance, reaction of 1-phenyl-1-cyclohexene (1r) and 1-methyl-1-cyclohexene (1s) offered the

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more stable trisubstituted olefins 3r and 3s by the selective β-H elimination (Table 3, entries 18
and 19).
3.4. Moβ catalyzed direct coupling reaction of styrene with various alcohols
The scope and limitations of the 10% Moβ catalyzed direct coupling reaction was further
extended to a variety of alcohols (Table 4). It is observed that benzhydrol having electron-
donating groups (-Me and -OMe) and halo group (-Cl) on the aryl ring were furnished the
subsequent products in good to excellent yields (Table 4, entries 1-4). 1-Phenylethanol and its
derivatives bearing electron-donating groups (-Me and -tert-butyl) and halo groups (-Br, -Cl and
–F) on the aryl ring were also gave the relevant products in good to excellent yields (Table 4,
entries 5-10). In addition, cyclic alcohol i.e. 1-indanol (2l) afforded the preferred product in
moderate yield (Table 4, entry 11). However, benzyl alcohol (2m) and cinnamyl alcohol (2n)
were unable to generate the corresponding products in the optimized reaction parameters (Table
4, entries 12 and 13).
Table 4 Alcohol variationa
Entry
1
Alcohol
Product
Time (h) Yieldb (%)
3
5
3
80
64
78
2b
3aa
3ab
c
2
3
2c
2d
3a

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4
5
3
80
61
78
76
75
76
70
57
2e
3ad
4
2f
3ae
6
4
2g
3af
7
4
2h
3ag
8
5
2i
3ah
9
5
2j
3ai
10
11
5
2k
3aj
4
2l
2m
2n
3ak
3al
12
13
12
12
00
00
3am
a
Reaction conditions: 1a (1 mmol), 2b-n (0.8 mmol), 10% Moβ (100 mg), 70 °C, sealed
vial. b Isolated yields based on alcohol.
3.5. Reaction mechanism
In order to obtain clear mechanistic insights into this reaction, few control experiments
were performed (see supporting information). Based on the findings and literature study [12-17],
two possible routes for this coupling reaction are recommended (Scheme 2). One possible route

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could be a direct alkylation of 1a with carbocation intermediate (A) (which is initially generated
by activation of 2a using zeolite) to produce carbocation intermediate (B), followed by
deprotonation to provide the desired product 3a. Another probable pathway is the generated
carbocation intermediate (A) reacts with 2a to form the corresponding dimeric ether (4a). The
ether 4a next reacts with 1a to generate the corresponding product 3a and along with alcohol 2a.
Ph
1a
Ph
Ph
Ph
Ph
+
-
-
-
+
+
-
Zeolite
+
+
H-Zeolite
H-Zeolite
Ph
Ph
Zeolite
Ph
Ph
+
-H2O
HO
Ph
Ph
3a
B
2a
A
2a
1a
Ph
Ph
-2a
Ph
O
4a
+
Ph
-
+
H-Zeolite
Scheme 2. Plausible mechanism for the direct coupling of olefins with alcohols.
To regenerate, the 10% Moβ was filtered to separate from the reaction mixture and
o
o
washed with ethyl acetate, dried at 100 C for 8 h and calcined at 450 C. Recyclability of the
10% Moβ catalyst was tested by performing the reaction of 1a with 2a in optimized reaction
parameters (Table S4). The recycled 10% Moβ catalyst exhibit constant activity up to five
cycles.
4. Conclusions
Briefly, we have developed the first example of zeolite catalyzed dehydrative cross-
coupling of alkenes and alcohols in solvent free environment. The current method presents an
attractive way to a wide variety of polysubstituted alkenes in good to excellent yields.

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Acknowledgements
We thank the DST, New Delhi for financial support under Indo-Russia (DST-RSF) (No.
INT/RUS/RSF/P-7) programme. Ch. D. and G. K. acknowledge the CSIR, India and K. S. and B.
R. acknowledge the UGC, India for financial support in the form of fellowship.
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 Moβ zeolite exhibits best catalytic activity towards the synthesis of internal olefins.
 The products obtained in moderate to excellent yields under solvent free conditions.
 The reused catalyst showed consistent activity up to five cycles.