The Henry reaction catalyzed by NiII and CuII complexes bearing arylhydrazones of acetoacetanilide

Article abstract of DOI:10.1016/j.jorganchem.2018.05.025

The new nickel coordination polymer [Ni(HL¹) (CH₃OH)₂]_n (1) and co-crystal H₃L¹?DMF (2) were obtained by reaction of NiCl₂·2H₂O with 2-(2-(1,3-dioxo-1-(phenylamino)but

Full text of DOI:10.1016/j.jorganchem.2018.05.025

Accepted Manuscript
II
II
The Henry reaction catalyzed by Ni and Cu complexes bearing arylhydrazones of
acetoacetanilide
Atash V. Gurbanov, Susanta Hazra, Abel M. Maharramov, Fedor I. Zubkov, Firudin I.
Guseinov, Armando J.L. Pombeiro
PII:
S0022-328X(18)30302-4
10.1016/j.jorganchem.2018.05.025
JOM 20459
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 3 May 2018
Revised Date: 28 May 2018
Accepted Date: 30 May 2018
Please cite this article as: A.V. Gurbanov, S. Hazra, A.M. Maharramov, F.I. Zubkov, F.I. Guseinov,
II
II
A.J.L. Pombeiro, The Henry reaction catalyzed by Ni and Cu complexes bearing arylhydrazones of
acetoacetanilide, Journal of Organometallic Chemistry (2018), doi: 10.1016/j.jorganchem.2018.05.025.
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Graphical Abstract

ACCEPTED MANUSCRIPT
II
II
The Henry reaction catalyzed by Ni and Cu complexes bearing
arylhydrazones of acetoacetanilide
a,b,
a
b
Atash V. Gurbanov, * Susanta Hazra, Abel M. Maharramov,
c
d,e
a,
Fedor I. Zubkov, Firudin I. Guseinov, Armando J. L. Pombeiro *
a
b
c
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–001 Lisbon, Portugal
Organic Chemistry Department, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan
Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-
Maklaya St., Moscow, 117198, Russian Federation
d
National University of Science and Technology «MISIS», Moscow Leninsky prosp. 4, 119049 Moscow, Russian Federation
Department of Chemistry, M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119992 Moscow, Russian Federation
e
*
Corresponding authors
Phone: +351 218419237
E-mail addresses:
organik10@hotmail.com (Atash V. Gurbanov)
pombeiro@tecnico.ulisboa.pt (Armando J. L. Pombeiro)
Abstract
1
1
The new nickel coordination polymer [Ni(HL )(CH OH) ] (1) and co-crystal H L ꢀDMF (2) were
3
2 n
3
obtained by reaction of NiCl ·2H O with 2-(2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)
2
2
1
hydrazineyl)benzoic acid (H L ) in the presence and absence of triethylamine, respectively, in a
3
mixture of methanol and dimethylformamide (DMF) (20:1, v/v). Reaction of CuCl ·2H O with
2
2
1
H3L in the presence of 2,2'-(methylazanediyl)bis(ethan-1-ol) (HR) in methanol yields
1
[
(
Cu(HR) (H L ) ] (3), whereas treatment of this copper salt with sodium 2-(2-(1,3-dioxo-1-
2
2
2
2
phenylamino)butan-2-ylidene)hydrazineyl)benzenesulfonate (NaH L ) in a mixture of acetone and
2
2
water (10:1, v/v) produces [Cu(HL )(H O) ]ꢀ2(H O)ꢀ{(CH ) C=O} (4). Compounds 1−4 were
2
2
2
3 2
characterized by IR and ESI-MS spectroscopies, elemental and X-ray crystal structural analyses,
and tested as catalyst for the Henry reaction of aliphatic and aromatic aldehydes with nitroethane in
different solvents such as acetonitrile, methanol or water. Good yields (up to 87%) and
diasteroselectivities (syn/anti 77:23) were observed in the reactions catalyzed by 3 in water.
II
II
Keywords: Ni and Cu complexes; arylhydrazones of acetoacetanilide; Henry reaction
1
. Introduction
The Henry (nitroaldol) reaction describes the catalytic coupling of a nucleophilic nitro alkane with
an electrophilic aldehyde or ketone to produce a highly synthetically useful β-nitroalcohol (Scheme
1) [1]. The prepared functionalized β-nitroalcohols represent important synthetic building blocks
that have been used in the syntheses of 2-amino alcohols, nitroalkenes, α-nitroketones,

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pharmaceutical substances, etc. [1-6]. Both deasterioselectivity and yield of β-nitroalcohols are
strongly depending on used catalysts. Up to now, many homogeneous catalysts, such as amberlyst
A-21 [7], cinchona alkaloid [8], alkali metal hydroxides, alkoxides or amines [7,9], a rhodium
complex in the presence of a silyl ketene acetal [10], heterobimetallic complexes with lanthanide
BINOL (BINOL = 2,2'-dihydroxy-1,1'-binaphthyl) systems [11], Mg–Al hydrotalcite [12,13],
guanidines [14], benzyltrimethylammonium hydroxide [15], proazaphosphatranes [16], Cu-
bis(oxazoline) [17] or Co-salen (salen = N,N'-bis(salicylidine)ethylenediamine) complexes [18,19]
Zn(II) dinuclear complexes [20,21] or a mixture of Zn(OTf) (OTf = triflate) and (+)-N-
2
methylephedrine [22], Zn(II)-1,3,5-triazapentadienato [23], etc. were used in the Henry reaction
between aldehydes and nitroalkanes. Most of these methods suffer from some
disadvantages/limitations, such as relatively high catalyst amount, long reaction time, toxic
solvents, narrow substrate scope, low reaction temperatures, use of additives, multistep synthetic
procedures for catalyst preparation, etc. Thus, the development of readily available, highly
deasteriostereoselective and cheaper catalysts for Henry reaction with a broad range of aldehyde
substrates is still highly desirable.
Scheme 1. The Henry (nitroaldol) reaction.
Arylhydrazones of active methylene compounds (AHAMC) and their complexes have
attracted much attention due to their useful properties such as catalysts, molecular switches,
III
II
II
II
II/IV
II
II
sensors, liquid crystals, etc. [24]. Ln, Fe , Zn , Cu , Ni , Sn , Co and UO complexes of
2
AHAMCs have already been applied as catalysts for C−C coupling of aldehydes with nitroalkanes
1
1
1
[
25]. Now, we herein report the use of [Ni(HL )(CH OH) ] (1), H L ꢀDMF (2) [Cu(HR) (H L ) ]
3 2 n 3 2 2 2
2
1
(
3) and [Cu(HL )(H O) ]ꢀ2(H O)ꢀ{(CH ) C=O} (4) (H L = 2-(2-(1,3-dioxo-1-(phenylamino)butan-
2 2 2 3 2 3
2
2
-ylidene)hydrazineyl)benzoic acid, NaH L = 2-(2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)
2
hydrazineyl)benzenesulfonate, HR = 2,2'-(methylazanediyl)bis(ethan-1-ol)) as the homogenous
catalysts for the Henry reaction of aliphatic and aromatic aldehydes with nitroethane to afford β-
nitroalcohols in high yields in water at room temperature.
2. Experimental
2.1. Materials and instrumentation
1
All the chemicals were obtained from commercial sources (Aldrich) and used as received. H L and
3
2
1
NaH L were synthesized according to the reported procedure [25g,26]. The H NMR spectra were
2
2

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TM
recorded at room temperature on a Bruker Avance II + 400 (UltraShield Magnet) spectrometer
operating at 400 MHz for proton. The chemical shift is reported in ppm using tetramethylsilane as
the internal reference. Elemental analyses (C, H, and N) were performed on a Finnigan EA 1112
instrument. Electrospray mass spectra (ESI-MS) were run with an ion-trap instrument (Varian 500-
MS LC Ion Trap Mass Spectrometer) equipped with an electrospray ion source. For electrospray
ionization, the drying gas and flow rate were optimized according to the particular sample with 35
p.s.i. nebulizer pressure. Scanning was performed from m/z 0 to 1200 in methanol solution. The
compounds were observed in the positive or negative mode (capillary voltage = 80−105 V).
2
2
0
.2. Synthesis
.2.1. Synthesis of 1 and 2
1
.1 mmol (33 mg) of H L were dissolved in 20 mL of methanol-dimethylformamide (20:1 v/v)
3
mixture, then 0.1 mmol (28 mg) of NiCl ꢀ2H O and 0.1 mL of triethylamine (in the case of 1) were
2
2
added and the system was stirred for 10 min. After ca. 3 d at room temperature, yellow (brown in
the case of 1) crystals precipitated which were then filtered off and dried in air.
1
: Yield, 55 %. Calcd. for C H N NiO (Mr = 446.09): C 51.16, H 4.75, N 9.42; found C 51.07,
19 21 3 6
+
H 4.63, N 9.36. MS (ESI, positive ion mode), m/z: 383.02 [Mr−2CH OH+H] . IR (KBr): 3458 (br)
3
–
1
ν(OH), 3008 ν(NH), 1676 (s) ν(C=O), 1592 ν(C=N) cm .
2
5
3
2
0
: Yield, 70 %. Calcd. for C H N O (Mr = 398.42): C 60.29, H 5.57, N 14.06; found C 60.22, H
20 22 4 5
+
.49, N 14.01. MS (ESI, positive ion mode), m/z: 326.20 [Mr−DMF+H] . IR (KBr): 3434 ν(H O),
2
–
1
241 ν(NH), 1696 and 1662 ν(C=O), 1599 ν(C=N) cm .
.2.2. Synthesis of 3
1
.1 mmol (33 mg) of H L were dissolved in 15 mL of methanol, then 0.1 mmol (17 mg) of
3
CuCl ꢀ2H O and 0.1 mmol (12 mg) of 12,2'-(methylazanediyl)bis(ethan-1-ol) were added and the
2
2
system was stirred for 10 min. After ca. 2 d at room temperature, greenish crystals precipitated
which were then filtered off and dried in air.
3
: Yield, 57 %. Calcd. for C H CuN O (Mr = 950.51): C 55.60, H 5.73, N 11.79; found C
44 54 8 12
55.53, H 5.67, N 11.72. MS (ESI, positive and negative ion modes), m/z: 150.54
2
+
1 −
[
Cu(C H N O ) ] and 324.30 [H L ] . IR (KBr): 3401, 3384 and 3372 (br) ν(OH), 3211 ν(NH),
1
0
26
2
4
2
–
1
1
2
0
669 (s) ν(C=O), 1600 ν(C=N) cm .
.2.3. Synthesis of 4
2
.1 mmol (38 mg) of NaH L were dissolved in 15 mL of acetone-water (15:1 v/v) mixture, then 0.1
2
mmol (17 mg) of CuCl ꢀ2H O was added and the system was stirred for 5 min. After ca. 3 d at
2
2
room temperature, brown crystals precipitated which were then filtered off and dried in air.
3

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4
: Yield, 49 %. Calcd. for C H CuN O S (Mr = 553.04): C 41.26, H 4.92, N 7.60; found C 41.22,
19 27 3 4
+
H 4.87, N 7.55. MS (ESI, positive ion mode), m/z: 423.90 [Mr−4H O−{(CH ) C=O}+H] . IR
2
3 2
–
1
(
KBr): 3420 (s, br) ν(OH), 3175 ν(NH), 1639(s) ν(C=O), 1598 ν(C=N) cm .
2.3. Crystal structure determination
X-ray diffraction patterns of 1−4 were collected using a Bruker SMART APEX-II CCD area
detector equipped with graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å) at room
temperature. Absorption correction was applied by SADABS [27,28]. The structure was solved by
2
direct methods and refined on F by full-matrix least-squares using Bruker's SHELXTL-97 [29]. All
non-hydrogen atoms were refined anisotropically. The details of the crystallographic data, selected
bond distances and angles for 1−4 are summarized in Tables S1-S3. Crystallographic data for the
structural analysis has been deposited to the Cambridge Crystallographic Data Center (CCDC
1
839644 for 3, 1833022 for 2, 1839643 for 3, and 1839645 for 4). Copy of this information can be
obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax:
+44) 1223-336033; E-mail: deposit@ccdc.cam.ac.uk or www.ccdc.cam.ac.uk/data_request/cif).
(
2.2. Catalytic activity studies
To a 10 mL vial were added the catalyst (1.0−6.0 mol%) and 2 mL solvent (CH Cl , MeCN or
2
2
MeOH) and the solution was stirred for 2 min at room temperature. Then, the aldehyde (1 mmol)
and nitroethane (4 mmol) were added and the resulting transparent homogeneous solution was
stirred at room temperature for the appropriate time. The solvent was removed under reduced
pressure and the resulting mixture was directly purified by column chromatography on silica gel
(petroleum ether/ethyl acetate = 6:1) to afford the Henry reaction product (isolated yield) [30]. The
analytical data of the obtained β-nitroalcohols are in good agreement with literature [31,32]. The
1
syn/anti diastereoselectivity of the β-nitroalcohols was determined by H NMR spectroscopy (in
CDCl ) based on the vicinal coupling constants of the products between the α-N−C−H and the α-
3
O−C−H [30−34].
3. Results and discussion
3.1. Synthesis and characterization of 1−4
1
Both ligands, 2-(2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)hydrazineyl)benzoic acid (H L )
3
and
sodium
2-(2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)hydrazinyl)benzenesulfonate
2
(
NaH L ), were reported earlier by some of us [25g,26]. Reaction of NiCl ·2H O with 2-(2-(1,3-
2
2
2
1
H3L in the presence and absence of triethylamine, in a mixture of methanol and
1
1
dimethylformamide (DMF) (20:1, v/v) leads to [Ni(HL )(CH OH) ] (1) and H L ꢀDMF (2),
3
2 n
3
respectively (Scheme 2). It has already been proved that the coordination ability of AHAMC can be
4

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improved by addition of a base to reaction mixture for a weakening of the resonance assisted
hydrogen bond (RAHB) in these ligands (Scheme 2) [24d,s]. Thus, only Fe(III)-AHAMC or Cu(II)-
AHAMC complexes can be obtained by direct reaction of metal salts with AHAMC [24s]. In order
to obtain other metal complexes of AHAMC ligands the base should be used for destroy strong
RAHB system (Scheme 2). Due to the strong coordination ability of the used auxiliary ligand, 2,2'-
1
(
methylazanediyl)bis(ethan-1-ol) (HR), the reaction of CuCl ·2H O with H L in the presence of
2
2
3
1
2+
HR in methanol yields [Cu(HR) (H L ) ] (3), which compoused by [Cu(HR) ] complex cation and
2
2
2
2
1
−
two anionic moieties [(H L ) ] (Scheme 2).
2
2
2
A monomeric complex [Cu(HL )(H O) ]ꢀ2(H O)ꢀ{(CH ) C=O} (4) was obtained by reaction
2
2
2
3 2
2
of CuCl ·2H O with NaH L in a mixture of acetone and water (10:1, v/v) (Scheme 2). The
2
2
2
compounds 1−4 are characterized by ESI-MS, IR spectroscopy, elemental analysis and single
crystal X-ray diffraction (see Tables S1-S3, Fig.). In the IR spectrum of 1, the ν(NH), ν(C=O) and
–
1
ν(C=N) signals appear at 3008, 1676 and 1592 cm , respectively, values that are significantly
1
shifted in relation to the corresponding signals of H L [3240 ν(NH), 1696 and 1663 ν(C=O), 1599
3
−
1
ν(C=N) cm ] [26], whereas same groups in 2 have similar signals at 3241 ν(NH), 1696 and 1662
–1
ν(C=O), 1599 ν(C=N) cm . In the IR spectrum of 3, the ν(NH) and ν(C=O) signals are also
–
1
significantly shifted: 3211 ν(NH) and 1669 (s) ν(C=O) cm . The IR spectrum of 4 shows ν(NH)
–
1
and ν(C=O) vibrations at 3175 and 1639 cm respectively, which significantly shift in relation to
2
−1
the corresponding signals of NaH L [2925 ν(NH) and 1669 ν(C=O) cm )] [25g]. Fragmentation
2
+
peaks in mass spectra of the compounds can be related as follows: 383.02 [Mr−2CH OH+H] (for
3
+
2+
1 −
1
), 326.20 [Mr−DMF+H] (for 2), 150.54 [Cu(C H N O ) ] and 324.30 [H L ] (for 3) and
10 26 2 4 2
+
4
23.90 [Mr−4H O−{(CH ) C=O}+H] (for 4). The elemental analyses are consistent with the
2 3 2
proposed formulations, which are also supported by X-ray crystallography (Fig.).
In 1, the nickel ion has a distorted octahedral coordination geometry with the chelating
hydrazone ligands occupying the four equatorial positions and the apical sites being engaged with
the methanol molecules (Fig.). The molecular structure of 2 contains two RAHB systems as well as
an intramolecular six-membered hydrogen-bonded ring. The asymmetric unit of 3 comprises one
1
–
2+
anionic (H L ) moiety with two RAHB systems and half of the [Cu(HR) ] complex cation, which
2
2
both units are gathered by intermolecular hydrogen interactions (Fig.).
5

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CH3
1
H
H
H
H3C
C H
6
CH3
N
C
5
O
1
O
O
O
O
H C
3
N
O
H
O
H
O
C
C
Ni
N
C
C6H5
i) MeOH-DMF
ii) NiCl 2H O
N
O
O
H
O
C
C
H
N
C
C
N
2
2
CH3
C
N
1
CH3
i) MeOH-DMF
2
ii) Et N
3
iii) NiCl 2H O
2
2
CH3
2+
C H
6
5
C H
6
5
N
Cu
N
N
O
N
O
O
N
O
N
O
H
C
C
H
X
i) MeOH
ii) CuCl 2H O
HO
HO
OH
OH
H
O
C
C
H
N
C
2
2
O
N
iii) CH N(CH CH OH)
C
C
3
2
2
2
CH3
CH3
2
CH3
1
X = COH (H L );
3
3
2
X = S(=O)ONa (NaH L )
2
C H H O
6
5
OH2
2
O
N
O
O
i) Acetone-H O
H
O
C
C
Cu
N
S
2
O
(2H O) (CH ) C=O
2 3 2
ii) CuCl 2H O
2
2
C
N
CH3
4
Scheme 2. Synthesis of 1−4.
1
2
6

ACCEPTED MANUSCRIPT
3
4
Fig. Crystal structures of 1−4 with partial atom numbering scheme. H-bond interactions are shown
as dashed blue lines.
3.2. Catalytic activity of 1-4 in the Henry reaction
1
2
Initially, 1, 2, 3, 4, NiCl ·2H O, CuCl ·2H O, H L and NaH L were screened in a model Henry
2
2
2
2
3
2
reaction between benzaldehyde and nitroethane in different solvents (dichloromethane, acetonitrile
and methanol) at room temperature and the results are listed in Table 1. Of these catalysts, 3 was
found to be the best for this reaction, affording the expected β-nitroalcohol product in 66% yield
with syn : anti = 73:27 in water after 24 h (Table 1, entry 25), what can eventually be associated to
the ionic character of this compound. No C−C coupling reaction between nitroethane and
benzaldehyde takes place in solvent-free conditions as well as in dichloromethane, acetonitrile and
methanol in the absence of catalysts (1−3) or metal salts (entries 1−5, 8). NiCl ·2H O, CuCl ·2H O,
2
2
2
2
1
2
H L and NaH L lead to the yield of β-nitroalcohols of 4−39 % in 24 h (entries 6,7, 9−16), what is
3
2
substantially lower than those obtained in the presence of complexes 1−3 in water (43−66 %,
entries 19, 25 and 28). Thus, 3 and water were chosen as the catalyst and sole solvent, respectively,
for further studies. The increase of reaction time from 0.5 h to 24 h led to higher conversion
(entries 1−6, Table 2), however the 4 h appears to be the optimal reaction time. To optimize the
catalyst loading, the reaction was carried out with different amounts of the catalyst and we found
that 4 mol % of the catalyst was required to give the best results (Table 2, entry 10). We have also
attempted to optimize the reaction by varying the temperature from 20ºC to 75ºC, which the yield of
β-nitroaldols insignificantly increase (from 79 to 85 %) and diasteroselectivity drops from syn : anti
=
74:26 to 72:28 in high temperature (Table 2, entries 10, 13−15). Furthermore, optimized reaction
condition was applied for solvent-free conditions (Table 2, entry 16), which provides low yield (41
).
%
7

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a
Table 1. Catalyst screening and optimization.
c
d
Entry
1
Catalyst
Blank
Solvent
No solvent
MeCN
Yield, %
−
Selectivity, syn/anti
−
b
2
3
4
5
6
7
8
9
−
−
−
−
4
9
−
7
−
−
−
−
Blank
MeOH
H O
2
MeCN
MeOH
NiCl ·2H O
60:40
60:40
−
2
2
H O
2
MeCN
MeOH
CuCl ·2H O
60:40
61:39
59:41
59:41
60:40
57:43
60:40
60:40
62:38
65:35
70:30
59:41
60:40
61:39
70:30
72:28
73:27
62:38
66:34
2
2
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
H O
MeCN
MeOH
11
5
26
35
9
2
1
H3L
H O
2
MeCN
MeOH
2
NaH2L
27
39
17
34
43
6
26
37
39
52
66
32
49
63
H O
2
MeCN
MeOH
1
2
3
4
H O
2
MeCN
MeOH
H O
2
MeCN
MeOH
H O
2
MeCN
MeOH
H O
2
70:30
a
1
2
Reaction conditions: catalyst precursor: NiCl ·2H O, CuCl ·2H O, H L , NaH L , 1, 2, 3 and 4 (1.0 mol%),
2
2
2
2
3
2
acetonitrile, methanol or H O (2 mL), nitroethane (4 mmol) and benzaldehyde (1 mmol), reaction time: 24h, reaction
2
o
b
c
1
temperature: 20 C. Solvent-free conditions, using nitroethane as solvent (2 mL), Determined by H NMR, based on
d
1
the starting benzaldehyde. Calculated by H NMR (see Experimental).
a
Table 2. Optimization of the Henry reaction condition catalyzed by 3.
b
c
Entry Time, h Amount of catalyst, mol%
Temp., ºC
Yield, %
Selectivity, syn/anti
74:26
1
2
3
4
5
6
0.5
1
2
4
6
4.0
4.0
4.0
4.0
4.0
4.0
20
20
20
20
20
20
39
55
67
79
79
79
74:26
74:26
74:26
75:25
24
75:25
7
8
9
1
1
1
6
6
6
6
6
6
1.0
2.0
3.0
4.0
5.0
6.0
20
20
20
20
20
20
66
72
76
79
80
80
73:27
74:26
75:25
75:25
75:25
75:25
0
1
2
1
1
1
3
4
5
6
6
6
4.0
4.0
4.0
35
55
75
82
84
85
73:27
73:27
72:28
d
1
6
6
4.0
20
41
74:26
a
Reaction conditions: 1.0−6.0 mol% of catalyst precursor (typically 5.0 mol%), H O (2 mL), nitroethane
4 mmol) and aldehyde (1 mmol). Isolated yields after column chromatography. Determined by H NMR.
Solvent-free conditions, using nitroethane as solvent (2 mL).
2
b
c
1
(
d
8

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In order to check the substrate scope of this C−C coupling reaction catalyzed by 3 with the
optimized conditions mentioned above, the reactions were carried out using various substrates. The
results are summarized in Table 3. A wide range of aromatic aldehydes participate well in this
reaction affording the corresponding β-nitroalcohols in moderate to good yields (65−87%) and
moderate diasteroselectivities (syn : anti = 72:28 − 75:25). The aromatic aldehydes with para
electron-withdrawing substituents show better yield than those with electron-donating substituents
(entries 1−7). It is worth noting that ortho-substituted aromatic aldehydes such as 2-
nitrobenzaldehyde and 2-methylbenzaldehyde, which are considered as sterically hindered substrates
also provided admirable yields of β-nitroalcohols (entries 8 and 9). Whereas, 2,4,6-
trimethylbenzaldehyde decreases the yield and diasteroselectivity of β-nitroalcohols (entry 10).
When aliphatic aldehydes propionaldehyde, butyraldehyde and pentanal were chosen as substrates
the reaction was much effective (Table 2, entries 11−13).
a
Table 3. Henry reaction of nitroethane with various aldehydes catalyzed by 3.
b
c
Entry
Substrate
4-(Dimethylamino)benzaldehyde
4-Methoxybenzaldehyde
4-Methylbenzaldehyde
Benzaldehyde
Yield, %
Selectivity, syn/anti
1
2
3
4
5
6
7
8
67
74
76
79
73:27
73:27
74:26
74:26
74:26
74:26
75:25
73:27
4-Bromobenzaldehyde
4-Chlorobenzaldehyde
4-Nitrobenzaldehyde
2-Nitrobenzaldehyde
81
82
84
82
9
2-Methylbenzaldehyde
79
73:27
1
1
1
1
0
1
2
3
2,4,6-trimethylbenzaldehyde
Propionaldehyde
Butyraldehyde
65
87
86
85
72:28
75:25
75:25
75:25
Pentanal
a
Reaction conditions: 5.0 mol% of catalyst 3, H O (2 mL), nitroethane (4 mmol) and aldehyde (1 mmol), reaction time:
h. Isolated yields after column chromatography. Determined by H NMR.
2
b
c
1
4
In comparison to other reported catalysts, such as lanthanide/sodium amide systems
(48−85%) [11], copper(II) complexes (70–77%) with amidoterephthalate [35], pyrrolidine-based
organocatalyst (67%) [36], scorpionate complex [NiCl{SO C(pzPh) }] (pz = pyrazolyl; 31.5% yield
3
3
for benzadehyde) [1q], 2-((E)-(((1S)-quinolin-4-yl(5-vinylquinuclidin-2-yl)methyl)imino) methyl)
phenol (72) [37], (S)-2-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)-6-(trifluoromethyl)
phenol (81) [43], etc. our complex 3 shows high catalytic performance in the C−C coupling of both
aliphatic and aromatic aldehydes with nitroethane.
4. Conclusions
II
II
II
Four new compounds, Ni -coordination polymer (1), co-crystal (2), Cu -ionic (3) and Cu -
mononuclear (4) complexes containing dicarboxylic- or sulfonic functionalized arylhydrazones of
acetoacetanilide have been synthesized by variation of reaction condition and structurally
9

ACCEPTED MANUSCRIPT
characterized. All compounds have been tested as homogeneous catalysts for the addition of
nitroethane to aliphatic or aromatic aldehydes producing the corresponding β-nitroalkanols (Henry
reaction). Ionic complex 3 was found to be the efficient catalyst for this C−C coupling reaction in
water (green solvent), producing β-nitroalcohols with good yields (65−87%) and
diastereoselectivities (syn/anti 75:25−72:28).
Acknowledgements
Authors are grateful to the Fundação para a Ciência e a Tecnologia (FCT) (project
UID/QUI/00100/2013), Portugal, for financial support. The publication was also prepared with the
support of the ''RUDN University Program 5-100''. Authors are thankful to the Portuguese NMR
Network (IST-UL Centre) for access to the NMR facility and the IST Node of the Portuguese
Network of mass-spectrometry for the ESI-MS measurements.
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Highlights
II
II
►
►
►
Ni and Cu complexes bearing arylhydrazones of acetoacetanilide
II
Ionic Cu complex shows high catalytic activity in Henry reaction
The catalytic activity depends on the nature of solvents, and water was chosen as green solvent