A NbO type Cu(II) metal-organic framework showing efficient catalytic activity in the Friedl?nder and Henry reactions

Article abstract of DOI:10.1039/c7dt01595j

A three-dimensional NbO type porous metal-organic framework 1 containing both tertiary amine groups and paddle wheel dinuclear Cu₂(COO)₄ secondary building units as the active centre was synthesized at room temperature. The activated

Full text of DOI:10.1039/c7dt01595j

View Article Online
View Journal
Dalton
Transactions
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: A. K. Gupta, D. De
and P. K. Bharadwaj, Dalton Trans., 2017, DOI: 10.1039/C7DT01595J.
This is an Accepted Manuscript, which has been through the
Volume 45 Number
1 7 January 2016 Pages 1–398
Royal Society of Chemistry peer review process and has been
accepted for publication.
Dalton
Transactions
Accepted Manuscripts are published online shortly after
An international journal of inorganic chemistry
www.rsc.org/dalton
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
rsc.li/dalton

Page 1 of 21
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01595J
A NbO type Cu(II) metal–organic framework showing efficient catalytic
activity in Friedländer and Henry reactions
Anoop K. Gupta, Dinesh De, Parimal K. Bharadwaj*
Department of Chemistry, Indian Institute of Technology Kanpur, UP-208016, India.
*E-mail: pkb@iitk.ac.in
Abstract: A three dimensional NbO type porous metal–organic framework 1 containing both
tertiary amine groups and paddle wheel dinuclear Cu2(COO)4 secondary building units as active
centre, was synthesized at room temperature. The activated framework 1′ can be used as efficient
heterogeneous catalyst for the synthesis of quinoline derivatives by Friedländer and Henry
(nitroaldol) reactions for the synthesis of β−nitroalcohols. This MOF-based heterogeneous
catalyst is easily recycled and reused further without losing its structural integrity and catalytic
activity.
Introduction
In recent years, there has been growing interest in the development of functional metal–
organic frameworks (MOFs),1 obtained by connecting metal ions/clusters with organic linkers.2
The porosity, channel shape, pore size and functionality of MOFs can be easily tuned by
judicious choice of metal nodes, organic ligands and synthetic strategies.3 Due to these
flexibilities, MOFs have emerged as novel porous materials with improved properties against its
conventional competitors such as zeolites and activated carbon.4 MOFs have shown enormous
potential in a wide range of applications such as catalysis,5 selective absorption and separation,6
magnetism,7 and molecular recognition.8 Among them, the utility of MOFs in catalytic reactions

Dalton Transactions
Page 2 of 21
View Article Online
DOI: 10.1039/C7DT01595J
is particularly interesting. Many organic reactions can be efficiently catalyzed by MOFs9 due to
accessibility of the active catalytic sites within the framework. MOFs can show its catalytic
activity through two different components, i.e., the metal ions and the coordinated linkers.10,2b
These two components decide its nature: either it is Lewis acidic or basic in the catalytic
medium.11 A literature survey will show that there are lots of examples of Lewis acidic metal
catalysis while the catalytic activity by Lewis basic nature of the MOFs remain scanty.12 For
example, Huh et al. reported a Lewis basic DABCO-functionalized Zn2+-MOF that catalyzed the
nitro-aldol reaction (known as Henry reaction) of 4-nitrobenzaldehyde with nitroalkanes.13 There
are various number of new methods being developed for functionalizing the linkers.14 The
heterogeneous catalysis by active Lewis basic organic functional groups in MOFs is still
challenging.15 Previously, our group reported a L-proline functionalized Cu2+-MOF where the L-
proline moiety with imidazole as a co-catalyst synergistically catalyzed the Baylis−Hillman
reactions.16
Generally, porous MOFs with high specific surface area and coordinatively unsaturated
metal centers (UMCs) are very good candidates for heterogeneous acidic catalysis.17 Among a
variety of MOFs, those with [Cu2(COO)4] paddle-wheel units containing one or more solvents
molecules loosely bound to the metals ions, have been explored as Lewis acidic catalysts in
many organic reactions.18 MOFs with basic functional groups, such as amido or amino groups in
the linkers are capable of functioning as Lewis basic heterogeneous catalysts.12 Besides, the
basic groups in the MOF may also exhibit selective gas adsorption.19
Earlier, we reported5b a chiral piperazine-derived ligand incorporating isophthalate units
at the terminals, i.e. 5,5′-(S)-(+)-2-methylpiperazine-1,4-diyl)diisophthalic acid. Herein, we
report a similar ligand i.e. 5,5'-(piperazine-1,4-diyl)diisophthalic acid (H4L; Scheme 1) that

Page 3 of 21
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01595J
produces a 3D Cu2+-MOF at room temperature and contains aqua bound paddle-wheel SBUs
with piperazine units within the pores of the framework.
Scheme 1. Schematic diagram of the ligand, H4L.
We show that the framework upon activation via heating forms 1′ having vacant
coordination sites on Cu2+ that can act as an excellent heterogeneous catalyst for Friedländer
reactions to synthesize quinoline derivative as well as for Henry reactions between aromatic
aldehydes and nitroalkanes.
Experimental
Materials and physical measurements. The details of materials used, physicochemical
characterization and X-ray structural investigation are given in the ESI†.
Synthetic methodology. The synthesis of the linker was achieved following previously reported
method20 and given in the ESI†.
Synthesis of {[Cu2(L)(H2O)2]·(3DMF)(4H2O)}n (1). Cu(NO3)2·3H2O (35 mg, 0.15 mmol) and
H4L (20 mg, 0.05 mmol) were taken in separate conical flasks and added 1mL water and 2mL
DMF to each. These solutions heated on the hot plate till clear solutions were obtained. Then
they were mixed and treated with two drops of conc. HCl and mixed well. The clear solution was

Dalton Transactions
Page 4 of 21
View Article Online
DOI: 10.1039/C7DT01595J
allowed to slowly evaporate at room temperature for 7 d. Blue crystals of 1 were obtained after
filtration. Yield = 57%. FT-IR (KBr pellets, cm-1): 3431 (broad), 2937 (m), 1662 (s), 1589 (s),
1414 (s), 1381 (s), 1280 (m), 1241 (m), 1149 (m), 1099 (s), 1001 (s), 777 (s), 732 (s), 662(m);
elemental analysis: calcd (%) for C14.5H23.5N2.5O8.5Cu: C 40.29, H 5.47, N 8.10; found: C 40.57,
H 5.83, N 8.27.
Results and discussion
Blue block-shaped crystals of 1 were obtained at room temperature by reacting the ligand
H4L and Cu(NO3)2·3H2O in aqueous DMF. The phase purity of the bulk sample was confirmed
by its powder X-ray diffraction pattern (Fig. S9, ESI†). Single-crystal X-ray diffraction study
revealed that 1 crystallized in the trigonal space group of R-3m (Table S1, ESI†) and was
isoreticular to NOTT-101.21 As expected, the framework was composed of paddle-wheel
4
-
dinuclear Cu2(COO)4 SBUs. Four SBUs were bridged by the ligand L to form a 3D NbO type
structure. Each Cu(II) centre in the SBU coordinated to four carboxylate oxygen and one water
molecule (Fig. 1a). The distances between Cu···O bonds lie in the range 1.930(5) Å to 2.160(6)
Å and the Cu···Cu distance is 2.642(2) Å. The packing of 1 along the crystallographic a or b axis
can be seen in Figure 1d. Two types of channels of different sizes could be seen along the c axis
(Fig. 1b). While the larger channel is surrounded by six paddle-wheel SBUs, the smaller one is
surrounded by three SBUs. There are two types of cages in the framework: one cage (pink) of
about 13.765 Å in diameter and the other large oval shaped cage of about 24.749 × 18.604 Å2 in
dimension (Fig. 1c) occupied by DMF and water as guest molecule which are quite disordered
and cannot be locate crystallographically. The solvent composition (1.5 DMF + 2 H2O molecule
per asymmetric unit) was confirmed from thermogravimetric and elemental analyses. The values

Page 5 of 21
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01595J
are in well-accordance with the PLATON-calculated solvent-accessible void volume, which is
found to be 68.64% of the unit-cell volume.
Fig. 1 Single-crystal X-ray diffraction structure showing (a) paddlewheel SBUs, (b) two types of
channels along the c-axis, (c) two different types of cages, and (d) packing of 1 along a- or b-
axis. The hydrogen atoms are omitted for clarity.
Catalytic activity towards the Friedländer and Henry reactions.
Recently, the MOF, NJU-Bai 19 with exactly the same ligand and structure has just been
reported, exhibiting enhanced CH4 storage.22 The permanent porosity of NJU-Bai 19 was
confirmed by N2 isotherm measurements at 77 K of the acetone solvent-exchanged sample. The

Dalton Transactions
Page 6 of 21
View Article Online
DOI: 10.1039/C7DT01595J
BET surface area of NJU-Bai 19 was calculated to be around 2803 m2 g−1, which are
comparable to those of NOTT-10121 (2805 m2 g−1). Our MOF 1 having similar structure but
different guest molecues in the voids was obtained via a different route and is expected to have
similar BET surface area. Due to this permanent porosity, availability of Lewis acidic Cu2+
catalytic sites and amine group incorporated linker within the framework, we probed its catalytic
activity towards Friedländer and Henry reactions.
Activation of 1 to produce the active catalyst, 1′. To activate the framework, the as-
synthesized sample was kept in acetone for 8 d at RT for solvent exchange. During this process,
acetone was refreshed once a day. The acetone exchanged sample was then heated to 120 °C
under ultra-high vacuum for 6 h to generate the fully de-solvated framework, 1′. The PXRD
pattern of 1′ (Fig. S11, ESI†) matches well with the as-synthesized MOF signifying that the
overall architecture of the framework remained intact upon solvent removal. Also, the TGA
o
curve showed the framework to be stable up to 280 C like the as-synthesized sample (Fig. S8,
ESI†)
Synthesis of quinoline derivatives via the Friedländer reaction. The large pore volume,
chemical and thermal stability, and ability to form an UMC makes the MOF a potentially good
heterogeneous catalyst. Here, we demonstrate the synthesis of quinoline derivatives via the
Friedländer reaction, catalyzed by 1′ (Scheme 2). Quinoline is an ubiquitous backbone in various
biologically and pharmaceutically active23 molecules. A variety of quinoline derivatives show
antibacterial, antimalarial, anti inflammatory agents besides exhibiting anti-asthmatic, anti-
hypertensive and tyrokinase PDGF-RTK inhibiting properties.24 Additionally, quinolines are
used as synthons for the synthesis of nanostructures and polymers which accompany the
optoelectronic or NLO properties with excellent mechanical strengths.25 Due to their importance

Page 7 of 21
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01595J
in industry, pharmacology and synthetic points of view, different versatile synthetic procedures
have been reported for the preparation of quinoline derivatives.26 Among these methods,
Friedländer hetero-annulation is simple and a direct route for the preparation of quinoline
derivatives through reaction between an aromatic 2-aminoaldehyde or ketone and a carbonyl
compound containing a reactive α-methylene group.27 Several new catalysts have been
developed for its synthesis that avoid the use of the traditionally basic conditions. Apart from
conventional protic acids, many other catalysts have also been used for the Friedländer
synthesis.28 Cu(BDC) and Cu(BTC) MOFs [BDC = 1,4-benzendicarboxylic acid, BTC = 1,3,5-
benzentricarboxylic acid] having vacant Cu(II) sites as Lewis-acid, have already been showed
catalytic activity for the Friedländer synthesis.29
Scheme 2. Synthesis of Quinoline derivatives through Friedländer reaction between aromatic 2-
aminoketone and carbonyl compound having α-methylene group.
The present study concerns the catalytic behavior of 1′ showing its huge potential as a
promising acidic heterogeneous catalyst for the synthesis of quinoline derivatives (Scheme 2). It
is shown in the Table 1 that the various aromatic 2-aminoketone (0.5 mmol) and different
carbonyl compounds containing a reactive α-methylene group (1-5 mmol) in presence of 1′ (5 wt
%) as a catalyst, under solvent-free conditions (except the reaction mixture containing 1,3-
cyclohexanedione), at 85 ºC for 24 h, give the quinoline derivatives as the expected product in

Dalton Transactions
Page 8 of 21
View Article Online
DOI: 10.1039/C7DT01595J
moderate to excellent yields. At first, we performed the reaction of 2-aminobenzophenone and
ethyl acetoacetate in the presence of 1′ at 85 ºC for 24 h. This reaction gave the desired
compound which was isolated with 94% yield (Table 1, Entry 1). The 4-chloro and 4-nitro
substituted 2-aminobenzophenone gave the product with 92% and 36% yields respectively
(Table 1, entries 2 and 3). Also, we tested the catalytic activity of 1′ with other ketones. 2-
aminobenzophenone reacted with acetylacetone and 1,3-cyclohexanedione afforded the products
with 91% and 87% yield, respectively (Table 1, entries 4 and 5). The heterogeneous catalytic
activity of 1′ showed superiority over homogeneous copper salts i.e. copper acetate (Table 1,
entry 6). The non-catalyst experiment showed that a very low yield (9%) was observed for 2-
aminobenzophenone with ethyl acetoacetate (Table 1, entry 7). Further, when the reaction
between 2-aminobenzophenone and ethyl acetoacetate was performed in the presence of
Cu(NO3)2.3H2O and ligand (H4L) under the same reaction condition, the desired compound was
obtained in 17 % yield (Table 1, entry 8). The reason for such a low yield is that the blockage of
the catalytic centers either by the nitrate anions, or by the ligands, which cannot be easily
accessed by the reactant molecules.29c These data show that 1′ is a highly proficient Lewis-acid
catalyst for Friedländer reactions with a wide variation of substrates. In each case, the desired
1
product was characterized by the H, 13C NMR and ESI mass spectroscopy (Fig. S12–S26,
ESI†).
Once the reaction was over, the reaction mixture was filtered to collect the catalyst. It
was washed by acetone and then heated at 120 ºC under vacuum for 2 h to regenerate the active
catalyst. We further used it for subsequent runs and checked its recyclability. The regenerated

Page 9 of 21
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01595J
Table 1. Screening for the 1′ catalysed Friedländer reaction between different aromatic 2-
aminoketone and different ketones at 80 ºCa
Aromatic 2- Carbonyl with α-
aminoketone methylene group
Quinoline
derivatives
Yield
(%)b
Entry
1
Catalyst
1′
94
2
3
1′
1′
92
36
4
5
6
7
1′
1′
91
87
47
9
Cu(OAc)2·H2O
No Catalyst
8
Cu(NO3)2·3H2O
+ H4L
17
aReaction conditions: 2-aminoaryl ketones (0.5 mmol), carbonyl compound having α-methylene
group (1-5 mmol), and catalyst 1′ (5 wt %), sealed tube 85 ºC for 24 h. bYield of the isolated
product after flash chromatography.

Dalton Transactions
Page 10 of 21
View Article Online
DOI: 10.1039/C7DT01595J
catalyst showed similar activity till at least four cycles (Fig. 2a); after that, it showed partial loss
in framework integrity as observed in the PXRD pattern (Fig. S27, ESI†). The heterogeneous
nature of 1′ was demonstrated by the hot filtration experiment (Fig. 2b).
Fig. 2 (a) Catalyst recyclability test and (b) hot filtration test showing heterogeneous nature of 1′,
in Friedländer reaction.
β−nitroalcohols Synthesis via carbon−carbon bond formation (Henry reaction). Further, the
catalytic activity of 1′ was evaluated in the Henry (or nitroaldol) reactions for the synthesis of
β−nitroalcohols. This reaction is an important C−C bond forming reaction.30 Besides,
β−nitroalcohols are often used as important starting materials for the synthesis of various
polyfunctional compounds having pharmaceutical significance.31 Generally, the Henry reaction
is efficiently catalyzed by basic catalysts32 and often leads a dehydrative nitro-olefin as a minor
byproduct.33 In addition, many homogenous catalyst based on homo / heterobimetallic34 and
transition-metal complexes have been applied in this reaction.35 Among them, the Cu(II)
complexes were proved to be one of the most efficient catalysts.36 However, only a few
heterogeneous catalysts for this reaction are reported till date.37 There are, also a few examples
of MOF-based heterogeneous catalysts for the Henry reaction.38 Since in our MOF, tertiary

Page 11 of 21
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01595J
amine group is incorporated in the linker and axially aqua bound Cu metal centre can be
activated to form active centre, which synergistically showed high efficiency for Henry reaction
under mild conditions.
Scheme 3 Henry reaction of substituted benzaldehydes with nitroalkanes catalyzed by 1′.
Here, we report the Henry (nitroaldol) reaction for the synthesis of β−nitroalcohols,
heterogeneously catalyzed by 1′ (Scheme 3). The screening results shows that the different
aromatic aldehyde (0.5 mmol) react with the nitroalkanes ( 10 mmol) in presence of 1′ (5 wt %)
under solvent free condition at 50 ºC for 48 h, to produce the corresponding product in good
yields, are summarized in Table 2. Initially we performed the reaction by using 4-
nitrobenzaldehyde as model substrate with nitromethane, and catalyst 1′. We observed that the
reaction afforded the corresponding nitroalcohol after 48 h in 89% yield (Table 2, entry 1). To
know the optimized reaction condition (Reaction time, catalyst’s amount, temperature), we
carried out the reaction between 4-nitrobenzaldehyde and nitromethane with 1′. The optimization
experiments revealed that the catalyst amount is 5 wt% and reaction time and temperature is 48 h
and 50 ºC, respectively (Fig. S50, ESI†). We also demonstrated the catalytic activity of 1′ with
others substituted aromatic aldehydes and nitromethane and nitroethane. Table 2 shows that on
reaction with nitromethane the product yield is 67% by benzaldehyde, 58% by 4-
methylebenzaldehyde, and 68% by 4-fluorobenzaldehyde ( Table 2, entries 4-6 respectivily)
while reaction with nitroethane the product yield is 81% by 4-nitrobenzaldehyde (Table 2, entry

Dalton Transactions
Page 12 of 21
View Article Online
DOI: 10.1039/C7DT01595J
7). The result summary unveiled that (i) aromatic aldehyde containing electron withdrawing
substituents affords higher yield (Table 2, entries 1, 2, 3 and 6) while aromatic aldehyde
containing electron donating substituents affords lower yield (Table 2, entry 5) with respect to
the benzaldehyde ( Table 2, entry 4). (ii) the size of the nitroalkane chain also alter the reactivity
due to steric factor,13 for example, on reaction with 4-nitrobenzaldehyde, nitromethane gave the
product in 89% yield while nitroethane gave the product in 81% yield (Table 2, entries 1 and 7).
Here we also checked the effect of substituents position, on the catalytic activity. The ortho,
meta, and para substituted nitrobenzaldehyde reacted with nitromethane and give the product in
82%, 86% and 89% yield respectively (Table 2, entries 2, 3, and 1). Also, we were performed
blank reaction (in absence of catalyst source; Table 2, entry 10) by using 4-nitrobenzaldehyde
and nitromethane as substrate at same reaction condition, very small amount of desired product
was obtained. The nitroaldol reaction also take place when using Cu(OAc)2·H2O and H4L as an
alternative of 1′ (Table 2, entries 8 and 9). Another set of reaction was examined between 4-
nitrobenzaldehyde and nitromethane in the presence of both Cu(NO3)2.3H2O and H4L at the
same reaction condition which gave the desired compound in 19% yield (Table 2, entry 11). This
result shows that the synergistic effect has been lost by the blocking of the catalytic sites on the
metal. Here, presumably only the basic nature of the ligand is operative for the reaction. These
results indicated the superiority over homogeneous copper salt and also showing the synergistic
effect of 1′ leading to high efficiency for Henry reaction.
The catalyst 1′ could be reused and recycled at least for four consecutive runs (Fig. 3a).
Crystallinity almost remains unchanged for three catalytic cycles and a slight degradation was
observed in the fourth cycle as proved by the PXRD analysis after each cycle (Fig. S49, ESI†).
The heterogeneous behavior of 1′ was confirmed using hot filtration test. The reaction mixture

Page 13 of 21
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01595J
Table 2. β−nitroalcohols synthesis of substituted benzaldehydes with nitroalkanes catalyzed by
1′.c
Entry
Catalyst
Ar−CHO
Nitroalkanes
Product
Yield
(%)d
1
2
3
89
82
86
1′
1′
1′
4
5
67
58
1′
1′
6
7
68
81
1′
1′
8
9
65
18
Cu(OAc)2·H2O
H4L
10
―
< 5
19
No Catalyst
Cu(NO3)2·3H2O
+ H4L
11
c Reaction Conditions: 5 mol% catalyst 1′, substituted benzaldehyde (0.5 mmol) and nitroalkane
(10 mmol), Reaction tube, 50 ºC for 48 h.
dYield of the isolated product after flash chromatography.
was filtered after 6 h to separate the catalyst. At same reaction condition, no further conversion
was observed in the filtrate part suggesting the heterogeneous nature of the 1′ (Fig. 3b). The

Dalton Transactions
Page 14 of 21
View Article Online
DOI: 10.1039/C7DT01595J
1
13
product formation was confirmed by the H, C NMR and ESI mass spectroscopy (Fig. S28–
S48, ESI†).
Fig. 3 (a) Reacyclability test of the nitroaldol reaction between 4-nitrobenzaldehyde and
nitromethane catalysed by 1′. (b) Plot of β−nitroalcohol yield vs time for the reaction between 4-
nitrobenzaldehyde and nitromethane in presence of 1′ (Black curve) and after filtering off the
catalyst 1′ (Red color).
Conclusions
In summary, a porous three dimensional NbO type metal−organic framework, 1 has been
synthesized in single crystal form from the assembly of a semi-rigid piperazine-derived ligand
and Cu(II) ion. The framework is isoreticular to NOTT-101 and is composed of paddle- wheel
dinuclear Cu2(COO)4 secondary building units. Coordinatively unsaturated Cu(II) sites, suitable
framework cages surrounded by tertiary nitrogen-containing ligands, and porosity, robustness
endow the framework 1′ as efficient heterogeneous catalyst for the synthesis of quinoline
derivatives by Friedländer reaction and β−nitroalcohols synthesis through the Henry (or
nitroaldol) reaction of substituted benzaldehydes with nitroalkanes.

Page 15 of 21
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01595J
Acknowledgements
We gratefully acknowledge the financial support received from the Department of Science and
Technology, New Delhi, India to P.K.B. and SRF from the CSIR to A. K. G. and D. D.
†Electronic supplementary information (ESI) available: The details of materials used,
physicochemical characterization and X-ray structural investigation. CCDC 1542257 for 1. For
ESI and crystallographic data in CIF or other electronic format see DOI:
References
1 (a) O. M. Yaghi, M. O’Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi and J. Kim, Nature,
2003, 423, 705–714; (b) K. Kim, Nat. Chem., 2009, 1, 603–604.
2 (a) D. Sun, Y. Ke, T. M. Mattox, S. Parkin and H. C. Zhou, Inorg. Chem., 2006, 45, 7566–
7568. (b) S. Horike, M. Dinca˘, K. Tamaki and J. R. Long, J. Am. Chem. Soc., 2008, 130, 5854–
5855.
3 (a) S. Kitagawa, R. Kitaura and S.-i. Noro, Angew. Chem., Int. Ed., 2004, 43, 2334–2375.
4 ( a) A. Zukal, I. Dominguez, J. Mayerová and J. Cezka, Langmuir, 2009, 25, 10314–10321; (b)
J. M. Ngoy, N. Wagner , L. Riboldi and O. Bolland, Energy Procedia, 2014, 63, 2230–2248.
5 (a) J. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen and J. T. Hupp, Chem. Soc.
Rev., 2009, 38, 1450–1459; (b) A. K. Gupta, D. De, R. Katoch, A. Garg and P. K. Bharadwaj,
Inorg. Chem., 2017, 56, 4698−4706.
6 (a) S. Sen, S. Neogi, A. Aijaz, Q. Xu, and P. K. Bharadwaj, Inorg. Chem., 2014, 53,
7591−7598; (b) P. Lama, A. Aijaz, S. Neogi, L. J. Barbour, and P. K. Bharadwaj, Cryst. Growth

Dalton Transactions
Page 16 of 21
View Article Online
DOI: 10.1039/C7DT01595J
Des., 2010, 10, 3410−3417; (c) L. Pan, B. Parker, X. Huang, D. H. Olson, J. Lee and J. Li, J.
Am. Chem. Soc., 2006, 128, 4180–4181.
7 (a) M. Kurmoo, Chem. Soc. Rev., 2009, 38, 1353–1379; (b) H. Miyasaka, M. Julve, M.
Yamashita and R. Clérac, Inorg. Chem., 2009, 48, 3420–3437; (c) M. C. Das, S. K. Ghosh, E. C.
Sanudo and P. K. Bharadwaj, Dalton Trans., 2009, 1644–1658.
8 (a) B. Chen, Y. Yang, F. Zapata, G. Lin, G. Qian and E. B. Lobkovsky, Adv. Mater., 2007, 19,
1693–1696; (b) A. K. Gupta, K. Tomar and P. K. Bharadwaj, CrystEngComm, 2017, 19, 2253–
2263. (c) B. Joarder, A. V. Desai, P. Samanta, S. Mukherjee and S. K. Ghosh, Chem.―Eur. J.,
2015, 21, 965−969.
9 (a) J. Y. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen and J. T. Hupp, Chem. Soc.
Rev., 2009, 38,1450–1459; (b) A. Dhakshinamoorthy, M. Opanasenko, J. Ćejka and H. Garcia,
Adv. Synth. Catal., 2013, 355, 247– 268; (c) A. Karmakar, H. M. Titi and I. Goldberg, Cryst.
Growth Des., 2011, 11, 2621–2636.
10 L. H. Wee, L. Alaerts, J. A. Martens and D. De Vos, Metal organic frameworks as catalysts
for organic reactions, Wiley-VCH, 2011, ch. 9, p. 191.
11 (a) D. Farrusseng, S. Aguado and C. Pinel, Angew. Chem. Int. Ed., 2009, 48, 7502 – 7513 (b)
J. S. Seo, D. Whang, H. Lee, S. I. Jun, J. Oh, Y. J. Jeon and K. Kim, Nature, 2000, 404, 982–
986; (c) R. Srirambalaji, S. Hong, R. Natarajan, M. Yoon, R. Hota, Y. Kim, Y. H. Ko and K.
Kim, Chem. Commun., 2012, 48, 11650–11652; (d) J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang
and C.-Y. Su, Chem. Soc. Rev., 2014, 43, 6011–6061.
12 (a) J. Gascon, , U. Aktay, M. D. Hernandez-Alonso, G. P.M. van Klink, F. Kapteijn, Journal
of Catalysis, 2009, 261, 75–87; (b) M. Savonnet, S. Aguado, U. Ravon, D. Bazer-Bachi, V.
Lecocq, N. Bats, C. Pinel and D. Farrusseng, Green Chem., 2009, 11, 1729–1732; (c) S.

Page 17 of 21
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01595J
Hasegawa, S. Horike, R. Matsuda, S. Furukawa, K. Mochizuki, Y. Kinoshita and S. Kitagawa, J.
Am. Chem. Soc., 2007, 129, 2607–2614.
13 J.-M. Gu, W.-S. Kim and S. Huh, Dalton Trans., 2011, 40, 10826–10829.
14 (a) L. Ma, C. Abney and W. Lin, Chem. Soc. Rev., 2009, 38, 1248–1256; (b) J. S. Costa, P.
Gamez, C. A. Black, O. Roubeau, S. J. Teat and J. Reedijk, Eur. J. Inorg. Chem., 2008, 1551–
1554.
15 D. Farrusseng, S. Aguado and C. Pinel, Angew. Chem., Int. Ed., 2009, 48, 7502–7513.
16 D. De, T. K. Pal and P. K. Bharadwaj, Inorg. Chem., 2016, 55, 6842−6844.
17 (a) A. Herbst, A. Khutia and C. Janiak, Inorg. Chem., 2014, 53, 7319−7333 (b) L. Alaerts, E.
Seguin, H. Poelman, F. Thibault-Starzyk, P. A. Jacobs and D. E. De Vos, Chem.―Eur. J., 2006,
12, 7353−7363.
18 (a) N. T. S. Phan, P. H. L. Vu and T. T. Nguyen, Journal of Catalysis, 2013, 306, 38–46; (b)
A. Dhakshinamoorthy, M. Alvaro and H. Garcia, Adv. Synth. Catal. 2009, 351, 2271–2276; (c) I.
Luz, F. X. L. Xamena and A. Corma, Journal of Catalysis, 2012, 285, 285–291; (d) D. Ruano,
M. Díaz-García, A. Alfayate and M. Sánchez-Sánchez, ChemCatChem, 2015, 7, 674–681.
19 D. De, T. K. Pal, S. Neogi, S. Senthilkumar, D. Das, S. S. Gupta and P. K. Bharadwaj,
Chem.―Eur. J., 2016, 22, 3387 – 3396.
20 Q. Mu, H. Wang, L. Li, C. Wang, Y. Wang and X. Zhao, Chem. ―Asian J., 2015, 10, 1864–
1869.
21 X. Lin, I. Telepeni, A. J. Blake, A. Dailly, C. M. Brown, J. M. Simmons, M. Zoppi, G. S.
Walker, K. M. Thomas, T. J. Mays, P. Hubberstey, N. R. Champness and M. Schröder, J. Am.
Chem. Soc. 2009, 131, 2159–2171.

Dalton Transactions
Page 18 of 21
View Article Online
DOI: 10.1039/C7DT01595J
22 M. Zhang, C. Chen, Q. Wang, W. Fu, K. Huang and W. Zhou, J. Mater. Chem. A, 2017, 5,
349–354.
23 (a) Y. L. Chen, K. C. Fang, J. Y. Sheu, S. L. Hsu and C. C. Tzeng, J. Med. Chem., 2001, 44,
2374–2377; (b) D. Doube, M. Bloun, C. Brideau, C. Chan, S. Desmarais, D. Eithier, J. P.
Falgueyeret, R. W. Friesen, M. Girad, Y. Girad, J. Guay, P. Tagari and R. N. Yong, Bioorg.
Med. Chem. Lett., 1998, 8, 1255–1260.
24 (a) B. Kalluraya and S. Sreenivasa, Farmaco, 1998, 53, 399–404; (b) G. Roma, M. D.
Braccio, G. Grossi and M. Chia, Eur. J. Med. Chem., 2000, 35, 1021–1035; (c) M. P. Maguire,
K. R. Sheets, K. Mcvety, A. P. Spada and A. Zilberstein, J. Med. Chem., 1994, 37, 2129–2137;
(d) O. Bilker, V. Lindo, M. Panico, A. E. Etiene, T. Paxton, A. Dell, M. Rogers, R. E. Sinden
and H. R. Morris, Nature, 1998, 392, 289–292.
25 (a) X. Zhang and S. A. Jenekhe, Macromolecules, 2000, 33, 2069–2082; (b) S. A. Jenekhe, L.
Luand, M. M. Alam, Macromolecules, 2001, 34, 7315–7324.
26 (a) V. V. Kouznetsov, L. Y.V. M´endez and C. M. M. Gòmez, Curr. Org. Chem., 2005, 9,
141–161; (b) G. Jones, in Comprehensive Heterocyclic Chemistry II, eds. A. R. Katritzky, C. W.
Reesand E. F. V. Scriven, Pergamon, NewYork, 1996, vol. 5, p. 167;(c) B. Jiang and Y.-G. Si, J.
Org. Chem., 2002, 67, 9449–9451; (d) R. H. F. Mansake and M. Kulka, Org. React., 1953, 7, 59;
(e) R. J. Linderman and K. S. Kirollos, Tetrahedron Lett., 1990, 31, 2689–2692.
27 (a) P. Friedländer, Ber., 1882, 15, 2572–2575; (b) C.-C. Cheng and S.-J. Yan, Org. React.,
1982, 28, 37.
28 (a) D. Yang, K. Jiang, J. Li and F. Xu, Tetrahedron, 2007, 63, 7654–7658; (b) S.
Ghassamipour and A. R. Sardarian, Tetrahedron Lett., 2009, 50, 514–519; (c) J. Marco-
Contelles, E. Pérez-Mayoral, A. Samadi, M. do Carmo Carreiras and E. Soriano, Chem. Rev.,

Page 19 of 21
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01595J
2009, 109, 2652–2671; (d) K. Niknam, M. A. Zolfigol and A. Dehghani, Heterocycles, 2008, 75,
2513–2521; (e) B. Das, M. Krishnaiah, K. Laxminarayana and D. Nandakumar, Chem. Pharm.
Bull., 2008, 56, 1049–1051; (f) J. Wu, H.-G. Xia and K. Gao, Org. Biomol. Chem., 2006, 4, 126–
129; (g) B. Jiang, J.-J. Dong, Y. Jin, X.-L. Du and M. Xu, Eur. J. Org. Chem., 2008, 2693–2696.
29 (a) E. Pérez-Mayoral, Z. Musilova, B. Gil, B. Marszalek, M. Polozij, P. Nachtigall and J.
Cejka, Dalton Trans., 2012, 41, 4036–4044; (b) N. T. S. Phan, T. T. Nguyen, K. D. Nguyen and
A. X. T. Vo, Appl. Catal., A, 2013, 464–465, 128–135; (c) E. Pérez-Mayoral and J. Cejka,
ChemCatChem, 2011, 3, 157–159.
30 (a) L. Henry, Bull. Soc. Chim. Fr., 1895, 13, 999–1003; (b) L.-X. Shi and C.-D. Wu, Chem.
Commun., 2011, 47, 2928–2930.
31 (a) N. Ono, The Nitro Group in Organic Synthesis; Wiley-VCH: New York, NY, 2001; (b) T.
Arai, Y. Taneda and Y. Endo, Chem. Commun., 2010, 46, 7936–7938;(c) I. Panov, P. Drabina, J.
Hanusek and M. Sedlák, Synlett, 2013, 24, 1280–1282; (d) P. Drabina, E. Horáková, Z.
Růžičková and M. Sedlák, Tetrahedron: Asymmetry, 2015, 26, 141–147.
32 F. A. Luzzio, Tetrahedron, 2001, 57, 915−945.
33 R. Ballini, G. Bosica and P. Forconi, Tetrahedron, 1996, 52, 1677–1684.
34 (a) H. Sasai, T. Tokunaga, S. Watanabe, T. Suzuki, N. Itoh and M. Shibasaki, J. Org. Chem.,
1995, 60, 7388–7389; (b) M. Shibasaki and N. Yoshikawa, Chem. Rev., 2002, 102, 2187–2210;
(c) D. Sureshkumar, K. Hashimoto, N. Kumagai and M. Shibasaki, J. Org. Chem., 2013, 78,
11494–11500.
35 (a) J. Dimroth and M. Weck, RSC Adv., 2015, 5, 29108–29113; (b) G.-H. Ouyang, Y.-M. He,
Q.-H. Fan, Chem.―Eur. J., 2014, 20, 16454–16457; (c) K. R. Reddy, C. V. Rajasekhar and G.
G. Krishna, Synth. Commun., 2007, 37, 1971–1976; (d) M. Bandini, F. Piccinelli, S. Tommasi,

Dalton Transactions
Page 20 of 21
View Article Online
DOI: 10.1039/C7DT01595J
A. Umani-Ronchi and C. Ventrici, Chem. Commun., 2007, 616–618; (e) J.-L. Li, L. Liu, Y.-N.
Pei and H.-J. Zhu, Tetrahedron, 2014, 70, 9077–9083.
36 (a) K. Matsumoto and S. Asakura, Tetrahedron Lett., 2014, 55, 6919–6921; (b) S. Jammi and
T. Punniyamurthy, Eur. J. Inorg. Chem., 2009, 2508–2511; (c) Y. Xiong, F. Wang, X. Huang, Y.
Wen and X. Feng, Chem.―Eur. J., 2007, 13, 829–833.
37 (a) R. Ballini, G. Bosica and P. Forconi, Tetrahedron, 1996, 52, 1677–1684; (b) K. K.
Sharma, A. V. Biradar, S. Das and T. Asefa, Eur. J. Inorg. Chem., 2011, 3174–3182.
38 (a) X.-M. Lin, T.-T. Li, Y.-W. Wang, L. Zhang and C.-Y. Su, Chem. ―Asian J., 2012, 7,
2796–2804; (b) J.-M. Gu, W.-S. Kim and S. Huh, Dalton Trans., 2011, 40, 10826–10829; (c) L.-
X. Shi and C.-D. Wu, Chem. Commun., 2011, 47, 2928– 2930; (d) A. Karmakar, S. Hazra, M. F.
C. Guedes da Silva, A. Paul and A. J. L. Pombeiro, CrystEngComm, 2016, 18, 1337–1349.

Page 21 of 21
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01595J
Table of Contents
A NbO type Cu(II) metal–organic framework showing efficient catalytic
activity in Friedländer and Henry reactions
Anoop K. Gupta, Dinesh De, Parimal K. Bharadwaj*
A three dimensional NbO type Cu(II)-MOF, 1 shows excellent and efficient heterogeneous
catalytic activity for Friedländer reaction as well as Henry reaction.