Showcasing research by Datta Markad and Sanjay K.

Mandal As featured in:

from Department of Chemical Sciences, Indian Institute of
Science Education and Research Mohali, India. Volume 47 Number 17 7 May 2018 Pages 5873–6252

Dalton
Synthesis and structural characterization of a novel dinuclear Transactions
Cu(II) complex: an efficient and recyclable bifunctional An international journal of inorganic chemistry
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heterogeneous catalyst for the diastereoselective Henry reaction

We are engaged in a major project to develop robust, efficient

and recyclable multifunctional heterogeneous catalysts
targeted for selected carbon-carbon bond forming organic
transformations. In the present work, we report a novel
bifunctional dinuclear Cu(II) complex containing a new flexible ISSN 1477-9226

PAPER

mixed pyridine-carboxylate ligand for the heterogeneous Zailai Xie et al.

Microporous carbons derived from organosilica-containing carbon dots
with outstanding supercapacitance

diastereoselective Henry (nitroaldol) reaction of aldehydes with

nitroethane. See Datta Markad and
Sanjay K. Mandal, Dalton Trans.,
2018, 47, 5928.

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Synthesis and structural characterization of a

novel dinuclear Cu(II) complex: an efficient and
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Cite this: Dalton Trans., 2018, 47,

5928 recyclable bifunctional heterogeneous catalyst for
Received 22nd February 2018,
Accepted 3rd April 2018 the diastereoselective Henry reaction†
DOI: 10.1039/c8dt00708j
Datta Markad and Sanjay K. Mandal *
rsc.li/dalton

We describe the synthesis and structural characterization of a
novel dinuclear Cu(II) complex containing a new flexible mixed
pyridine-carboxylate ligand. Single crystal X-ray diffraction reveals
its uniqueness with two coordinated water molecules and four
uncoordinated pyridyl groups. Utilizing the bifunctional catalytic
sites, it has been found to be an efficient, robust and recyclable
heterogeneous catalyst for the diastereoselective Henry (nitroal-
dol) reaction of aldehydes with nitroethane.
The diastereoselective Henry (nitroaldol) reaction is one of the
most powerful and efficient reactions for the construction of a
C–C bond.1–3 It provides a straightforward entry to diastereo-
merically enriched β-nitroalcohols, generating a number of
intermediate compounds with potential demands in industrial
as well as biological applications and thus playing a vital role
in synthetic organic chemistry.4,5 The corresponding products
of this reaction can easily be transformed into 2-hydroxy car-
boxylic acids, 2-nitro ketones, nitro alkenes and β-amino
alcohols.6–11 With perfect atom efficiency as well as synthetic
utility of the products, this area has substantially advanced
over the last few decades. The reaction of a nitroalkane (other
than nitromethane) with benzaldehyde produces two new
stereocenters, suffering from a low reactivity and poor
diastereoselectivity.
Enormous efforts have been made on the development of
Henry reaction using bases, solid-supported bases, organo-
catalysts, biocatalysts, metal salts, transition metal complexes,
and coordination polymers/metal–organic frameworks.1,5,12–32
Among them, the utilization of metal-based catalysts has
attracted considerable attention, as these inhibit undesirable
side reactions, such as dehydration of β-nitroalcohol, conden-
sation of aldehydes bearing α-hydrogen, and epimerization. In
1995, Shibasaki et al.18 demonstrated the first syn-selective and
enantioselective nitroaldol reaction catalysed by hetero-bi-
metallic catalysts. In recent years, the Cu-catalyzed Henry reac-
tion has received special attention.22–27 Even though impress-
ive progress has been made, there is still scope to develop new
catalysts with unique features for the diastereoselective Henry
reaction of aldehydes with nitroethane. Generally, the Henry
reaction involves the addition of a nitronate ion to a carbonyl
compound.3 A nitronate ion can be generated in situ by the
deprotonation of a nitroalkane with an external base. The
addition is facilitated either by a Lewis acid catalyst or by a
suitable bifunctional catalyst; the former catalyst activates the
carbonyl partner and the latter works as a combination of
Lewis acid-Brønsted base that activates and brings both reac-
tants together.20
Based on the strategic design, herein we report a new mixed
pyridine-carboxylate ligand H2(4-BPDC) (N,N’- bis (4-pyridyl-
methyl)-1,4-diaminobutane-N,N’-diaceticacid), in which each
of the two identical ends is linked with a flexible tetra-methyl-
ene chain, and its dinuclear Cu(II) complex, [Cu2(4-BPDC)2
(H2O)2]·9H2O (1) as shown in Scheme 1. Based on the single
crystal structure of 1, the Cu(II) centres provide Lewis acidic
sites, while the four uncoordinated pyridyl groups act as mod-
erately Brønsted basic sites that will facilitate the deprotona-
tion of nitroethane (a prerequisite) for the Henry reaction
(Fig. 1a). Thus, the use of 1 as an efficient and recyclable

Department of Chemical Sciences, Indian Institute of Science Education and

Research Mohali, Sector 81, Manauli PO, S.A.S. Nagar, Mohali, Punjab 140306,
India. E-mail: sanjaymandal@iisermohali.ac.in
† Electronic supplementary information (ESI) available: Synthesis of H2(4-BPDC)
and 1, additional figures and tables (NMR, SCXRD). Crystallographic data of 1 in
CIF format. CCDC 1824627. For ESI and crystallographic data in CIF or other Scheme 1 Synthesis of 1 from H2(4-BPDC) and Cu(ClO4)2·6H2O under
electronic format see DOI: 10.1039/c8dt00708j ambient conditions.

5928 | Dalton Trans., 2018, 47, 5928–5932 This journal is © The Royal Society of Chemistry 2018

Dalton Transactions
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Fig. 1 (a) Single crystal structure of 1 with labelled bifunctional catalytically active sites in it. (b) View of 3D supramolecular architecture of 1 along
the c-axis.
heterogeneous bifunctional catalyst for the Henry reaction is
demonstrated.
The ligand H2(4-BPDC) was synthesized in two steps (see
the ESI† for details) and characterized by 1H and 13C NMR
spectroscopy and HRMS (see Fig. S1–S5, ESI†). Treatment of
Cu(ClO4)2·6H2O with H2(4-BPDC) (at a 1 : 1 ratio) in methanol
under ambient conditions affords 1 as a bluish green precipi-
tate in 71% yield. Compound 1 is insoluble in MeOH, EtOH,
i
PrOH, CH3CN, EtOAc and CH2Cl2 but soluble in water, DMF
and DMSO. Using FTIR spectroscopy, the asymmetric and sym-
metric stretching frequencies for the carboxylate, which appear
at 1626 cm−1 and 1375 cm−1, respectively, (νasym − νsym =
251 cm−1), confirm its monodentate binding mode in 1
(Fig. S6, ESI†). It shows reasonable thermal stability based on
the thermogravimetric analysis (Fig. S7, ESI†). In a two-step
process, nine lattice water molecules (14.8%, calc. vs. 14.8%,
obs) are lost first followed by two coordinated water molecules
(3.3%, calc. vs. 3.9%, obs) with further decomposition at
225 °C. This could be due to the intermolecular hydrogen
bonding between lattice water and coordinated water mole-
cules which results in a supramolecular network (vide infra).
Single crystals of 1 were obtained from the slow evaporation
of its aqueous solution. The single crystal X-ray diffraction
study33 reveals that 1 crystallizes in the monoclinic space
group C2/c with Z = 4. The asymmetric unit consists of one
4-BPDC, two crystallographically independent Cu(II) ions with
half occupancies and two coordinated water molecules with
half occupancies. Both Cu1 and Cu2 adopt a slightly distorted
square-pyramidal geometry (τ parameter: 0.24 and 0.26,
respectively)34 with an N2O3 environment where each Cu(II)
centre is surrounded by two oxygen atoms, two nitrogen atoms
from two different 4-BPDC ligands and one oxygen atom from
the water molecule. The coordinated water molecule occupies
the apical site of both Cu(II). An asymmetric unit and a coordi-
nation environment around the Cu(II) centers with atom label-
ling are shown in Fig. S8.† The Cu–N and Cu–O distances are
in the range of 2.043(3)–2.052(2) Å and 1.938(2)–2.261(5) Å,
respectively. In 1, the Cu1⋯Cu2 distance is 6.780 Å. Crystal
data and structure refinement and the selected bond distances
and angles are listed in Tables S1 and S2, respectively, ESI.†
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A 14-membered rectangular ring involving two copper
centers, four alkyl nitrogen atoms and eight methylene groups
of two 4-BPDC ligands (dimensions: 3.89 Å × 6.78 Å) is formed.
Each hydrogen atom of one of the coordinated water mole-
cules (O5) is involved in intermolecular bifurcated hydrogen
bonding with the uncoordinated oxygen (O1) of the carboxylate
group (O5–H5⋯O1: d/Å: 2.04(4), θ/°: 172(4)), whereas the
hydrogen atoms of the other coordinated water molecule (O6)
do not participate in hydrogen bonding. Interestingly, all four
pyridyl nitrogen atoms are neither coordinated to Cu(II) nor
participated in hydrogen bonding. Furthermore, the hydrogen
atoms of methylene groups (C2 and C4) form hydrogen bonds
with carboxylate oxygen atoms (O4) to generate a 3D supramo-
lecular architecture (Fig. 1b and Fig. S9, ESI†). The hydrogen
bond parameters are listed in Table S3, ESI.† The experimental
powder X-ray diffraction (PXRD) pattern of 1 matched perfectly
with the simulated pattern (from the SCXRD) confirming its
bulk phase purity (Fig. S10, ESI†).
The as-prepared 1 was employed as a heterogeneous catalyst
for the Henry reaction without any prior treatments. It was
expected that the water molecules could easily be exchanged
with the reactants during the reaction. Initial optimization
studies were undertaken by using 4-nitrobenzaldehyde and
nitroethane as substrates under various reaction conditions
which are given in Table 1. In a typical reaction, a mixture of
aldehyde (0.1 mmol), nitroethane (0.3 mmol), catalyst and
solvent (1 mL) taken in a capped glass vessel was stirred at a
particular temperature for a period of time. The mixture was
then centrifuged and filtered to remove the solid catalyst.
Evaporation of the solvent from the filtrate gave the crude
product, which was a mixture of the β-nitroalkanol diastereo-
isomers (syn and anti-forms, with the predominance of the
former) and the product was analysed by 1H NMR spectroscopy
(Fig. S11, ESI†). All three factors (temperature, solvent and
catalyst amount) significantly influenced the reaction. When
2 mol% of the catalyst was used at 28 °C in methanol, a con-
version of 52% (syn/anti: 52/48) of 4-nitrobenzaldehyde into
β-nitroalkanol was achieved after 36 h (Table 1, entry 1). Upon
increasing the reaction temperature to 70 °C, the reaction yield
increased drastically (80%, syn/anti: 52/48) (Table 1, entry 2).
Dalton Trans., 2018, 47, 5928–5932 | 5929
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Table 1 Optimization of reaction conditions for the Henry reaction of

4-nitrobenzaldehyde and nitroethane catalyzed by 1 a

Fig. 2 (a) A plot of yield vs. time (blue curve) for 1; its heterogeneous
Time Catalyst Yieldb Selectivity nature is demonstrated by its removal from the reaction mixture at 12 h
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Entry (h) Solvent (mol%) (%) (syn/anti) followed by further stirring until 36 h (brown line). (b) Catalyst recyclabil-
ity test in the Henry reaction.
c
1 36 CH3OH 2 52 52/48
2 36 CH3OH 2 80 52/48
3 36 CH3OH 3 94 58/42
4 36 CH3OH 4 97 62/38 Control reactions were carried out with the precursors of 1
5 36 CH3OH 5 98 56/44
6 42 CH3OH 4 98 58/42
(Cu(ClO4)2·6H2O and H2(4-BPDC)) where the obtained reaction
7c 36 CH3OH 4 81 56/44 yields were much lower than that using 1 (Table 1, entries 19
8 36 CH3CN 4 32 53/47 and 20). A blank test with 4-nitrobenzaldehyde was performed
9 36 C2H5OH 4 88 63/37
10 36 i
PrOH 4 83 57/43
without 1 at 70 °C in methanol and no β-nitroalkanol was
11 36 CH2Cl2 4 83 59/41 detected after a reaction time of 36 h (Table 1, entry 21). In
12 36 EtOAc 4 51 53/47 comparison with other reported metal catalysts for the
13 36 — 4 65 56/44
14 6 CH3OH 4 65 56/44
diastereoselective Henry reaction, catalyst 1 is among the best
15 12 CH3OH 4 72 52/48 ones23–27 (Table S4, ESI†) in terms of catalyst loading, reaction
16 18 CH3OH 4 79 56/44 conditions, yield combined with diastereoselectivity and
17 24 CH3OH 4 83 57/43
18 30 CH3OH 4 91 60/40
recyclability (vide infra). More importantly, the ratio of the sub-
19_Cu(ClO4)2·6H2O 36 CH3OH 4 31 52/48 strates (4-nitrobenzaldehyde to nitroethane) used in the case
20_H2(4-BPDC) 36 CH3OH 4 04 74/26 of catalyst 1 (1 : 3) is the lowest compared to those used for
21_Blank 36 CH3OH — 00 —
similar catalysts (1 : 4 or 5) listed in Table S4.† Interestingly,
a
Reaction conditions: 2.0–5.0 mol% of a catalyst, solvent (1 mL), only one homodinuclear Cu(II) complex and few mononuclear
nitroethane (0.3 mmol) and 4-nitrobenzaldehyde (0.1 mmol) at 70 °C. Cu(II) complexes have been reported so far for the diastereo-
b
Determined by 1H NMR analysis (see the Experimental section, ESI).
c
Reaction carried out at 28 °C. selective Henry reaction of 4-nitrobenzaldehyde and
nitroethane. For example, a homodinuclear Cu(II) complex
containing a bis (2-pyridyl)oxalohydrazide ligand (no crystal
structure is reported)24 promoted this reaction with 8 mol%
The increase in yield motivated us to perform the reaction at catalyst (8 h, 45 °C, and reaction media: methanol/water) in
70 °C. By keeping this temperature constant and varying the 93% yield (syn/anti: 73/27). On the other hand, 3 mol% of a
catalyst amount from 2 mol% to 5 mol%, it was observed that mononuclear Cu(II) complex of 2-propionamidoterephthalate
4 mol% catalyst afforded high yield and excellent diastereo- but containing four coordinated water molecules25 provided
selectivity (97%, syn/anti: 62/38) (Table 1, entries 3–5). 94% yield (syn/anti: 80/20) in 30 h (reaction medium: water) at
Furthermore, upon increasing the reaction time to 42 h, there the same temperature used for catalyst 1. Two other mono-
was no significant change in yield but diastereoselectivity nuclear Cu(II) catalysts with either a sterically hindered
decreased (Table 1, entry 6). ligand26 or even without a ligand other than water23 did not
Among all solvents used, the highest yield and diastereo- provide better results than catalyst 1; in fact, the latter
selectivity (97%, syn/anti: 62/38) were obtained in methanol complex, [(S)-H2mpz][Cu(H2O)4](SO4)2·2H2O, where mpz = (S)-
(Table 1, entries 8–12). This also reveals that the yield depends 2-methylpiperazine, containing the tetra(aqua)Cu(II) cation,
on solvent polarity – low yields are observed in less polar sol- provided the anti product exclusively but in only 35% yield
vents. In all solvents, the catalytic reaction is heterogeneous in (24 h, 20 °C, 2 mol% catalyst and reaction medium: metha-
nature. To investigate the advantageous role of neat con- nol). Finally, among many CP and MOF based catalysts where
ditions, we carried out the above reaction without any solvent diastereoselectivity was reported a μ1,5-dicyanamide bridged
under identical conditions. This afforded the corresponding 1D CP of Cu(II)27 required less catalyst concentration but more
β-nitroalkanol product in moderate yield (65%, syn/anti: 56/44) time and the higher substrate ratio (1 : 4) than catalyst 1. For
(Table 1, entry 13). The reaction was time dependent, and a those CPs and MOFs where no diastereoselectivity has been
decrease in reaction time leads to a significant decrease in the reported,29–32 the ratio of the substrates (4-nitrobenzaldehyde
conversion (Table 1, entries 14–18). A plot of yield versus time to nitroethane) used is very high ranging from 1 : 20 to 1 : 160.
for the reaction of 4-nitrobenzaldehyde and nitroethane is pre- Furthermore, our catalyst is made under ambient conditions
sented in Fig. 2a. with readily available and cheap starting materials, which

5930 | Dalton Trans., 2018, 47, 5928–5932 This journal is © The Royal Society of Chemistry 2018
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provide added advantages over some expensive and enantio-
differentiating catalysts.
After obtaining optimum conditions for the catalytic reac-
tion (4.0 mol% of 1, aldehyde (0.1 mmol), nitroethane
(0.3 mmol) at 70 °C in MeOH (1.0 mL) for 36 h), the efficacy of
catalyst 1 in the Henry reaction was evaluated for a wide range
of substrates. Desired products were isolated in moderate to
good yields (Table 2). The catalyst is capable of activating the
substrates containing various groups, such as –CH3, –OCH3,
–NO2, –CN, –F, –Cl and –Br (Table 2, entries 2–11). The nature
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Comparison of PXRD patterns, IR and UV-Visible spectra (see
Fig. S12–S14,† respectively) of the pristine and recovered cata-
lyst persuasively demonstrated the retention of structural
integrity of 1 after reactions.
To clarify whether the catalytic process is heterogeneous or
homogeneous, the hot filtration experiment was conducted. A
control experiment was performed with catalyst 1 until an
intermediate yield (ca. 72%) was observed (12 h) and then the
catalyst was removed by centrifugation and filtration. The cata-
lyst-free reaction solution was stirred under the same con-

of substrates greatly influences the yield and selectivity. It is
reasonable to conclude from the above results that the elec-
tron-withdrawing groups enhance the reactivity and electron-
releasing groups reduce the reactivity. In view of this, a mecha-
nism is proposed in Scheme S1,† also confirming the obser-
vation by Shibasaki18 for the homodinuclear metal complexes.
The broad substrate generality and operational simplicity of
the present heterogeneous syn-selective nitroaldol protocol are
particularly valuable for the synthesis of enantio-enriched 1,2-
amino alcohols, which constitute a versatile substructure in
medicinal chemistry.
The catalyst 1 is easily recoverable by filtration and can be
reused several times without any significant loss of catalytic
activity. After the first cycle, the catalyst was recovered by cen-
trifugation and then washed thoroughly with methanol and
air-dried. The performance of the recycled catalyst in the
Henry reaction up to five successive runs is shown in Fig. 2b.
The catalytic efficiency of the recovered catalyst remained
almost the same in every run. To check the stability of the
recovered catalyst, the spent catalyst was thoroughly character-
ized by PXRD, and FTIR and UV-Visible spectroscopy.
Table 2 Substrate scope in the Henry reaction catalyzed by 1 a
ditions for an additional 24 h. As shown in Fig. 2a (brown
line), after removal of the solid catalyst, the yield of products
did not increase significantly. These results demonstrate that
the catalysis is heterogeneous in nature. Additionally, the fil-
tered solution after the separation of the catalyst was evapor-
ated to dryness and the amount of Cu(II) was determined
using Energy-dispersive X-ray (EDX) spectroscopy. Only 0.01%
of Cu(II) was found, thus ruling out any significant leaching of
the catalyst (Fig. S15, ESI†).
In summary, we have demonstrated that an appropriate
design of mixed organic ligands (a combination of pyridyl and
carboxylate groups) can be employed to construct a novel
dinuclear Cu(II) complex 1 possessing the features needed for
effective catalysis, i.e., fully reactant accessible active metal
sites and the presence of uncoordinated four pyridyl groups as
Brønsted basic sites. It has been efficiently used as a bifunc-
tional heterogeneous catalyst for the syn-selective
β-nitroalcohol synthesis through the Henry reaction of substi-
tuted benzaldehydes with nitroethane in high yield (up to
97%). Our study further shows that it is heterogeneous in
nature and recyclable up to five consecutive cycles without loss
of activity. Appropriate modifications in the ligand system, par-
ticularly chiral center(s), are currently being pursued in our
laboratory for improving efficacy and diversity.

Conflicts of interest
There are no conflicts to declare.

Yieldb Selectivity
Acknowledgements
Entry Aldehyde (%) (syn/anti) TONc
Funding for this work was provided by IISER, Mohali. D. M. is
1 Benzaldehyde 90 62/38 22 grateful to the UGC of India for a research fellowship. The use
2 4-Methylbenzaldehyde 78 56/44 19
3 4-Methoxybenzaldehyde 44 59/41 11 of X-ray and NMR central facilities and other departmental
4 4-Flurobenzaldehyde 89 58/42 22 facilities at IISER Mohali is acknowledged.
4 4-Chlorobenzaldehyde 89 55/45 22
6 4-Bromobenzaldehyde 92 58/42 23
7 4-Cyanobenzaldehyde 93 54/46 23
8
9
4-Nitrobenzaldehyde
3-Methoxybenzaldehyde
97
77
62/38
59/41
24
19
Notes and references
10 3-Chlorobanzaldehyde 92 56/44 23
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Reaction conditions: 4.0 mol% of catalyst 1, aldehyde (0.1 mmol), 2 N. Ono, The nitro group in organic synthesis, Wiley-VCH,
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Calculated by 1H NMR. c Number of moles of β-nitroalkanol per mole New York, 2001.
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33 Crystal data for 1: C40H52Cu2N8O10, Mr = 1035.57, T =
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c = 19.2926(15) Å, α = 90°, β = 93.630(5)°, γ = 90°, V =
4943.8(7) Å3, Z = 4, Dc = 1.252 g cm−3, μ = 0.917 mm−1,
Rint = 0.0312, final R1 = 0.0457, wR2 = 0.1384 for 3368
unique reflections (I > 2σ(I)). Full details are summarized
in Table S1.†
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