Nitroaldol reaction catalyzed by arylhydrazone di- and triorganotin(IV) complexes

Article abstract of DOI:10.1016/j.jorganchem.2017.09.044

Two known organotin(IV) complexes, [Sn(C₆H₅)₃HL¹] (1, H₂L¹ = 2-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)benzoic acid) and [Sn(C₂H₅)₂(1κO,2κO-H₃L<

Full text of DOI:10.1016/j.jorganchem.2017.09.044

Accepted Manuscript
Nitroaldol reaction catalyzed by arylhydrazone di- and triorganotin(IV) complexes
Atash V. Gurbanov, M.Fátima C. Guedes da Silva, Leonid M. Kustov, Firudin I.
Guseinov, Kamran T. Mahmudov, Armando J.L. Pombeiro
PII:
S0022-328X(17)30575-2
10.1016/j.jorganchem.2017.09.044
JOM 20119
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 7 August 2017
Revised Date: 25 September 2017
Accepted Date: 29 September 2017
Please cite this article as: A.V. Gurbanov, M.Fá.C. Guedes da Silva, L.M. Kustov, F.I. Guseinov, K.T.
Mahmudov, A.J.L. Pombeiro, Nitroaldol reaction catalyzed by arylhydrazone di- and triorganotin(IV)
complexes, Journal of Organometallic Chemistry (2017), doi: 10.1016/j.jorganchem.2017.09.044.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Nitroaldol reaction catalyzed by arylhydrazone
di- and triorganotin(IV) complexes
Atash V. Gurbanov,a,b,c M. Fátima C. Guedes da Silva,a Leonid M. Kustov,d,e
Firudin I. Guseinov,d,e Kamran T. Mahmudov,a,c,f,* Armando J. L. Pombeiroa,*
a Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–001 Lisbon, Portugal
b Organic Chemistry Department, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan
c Organic Chemistry Department, RUDN University, 6 Miklukho-Maklaya str., Moscow 117198, Russian Federation
d National University of Science and Technology «MISIS», Moscow Leninsky prosp. 4, 119049 Moscow, Russian Federation
e Department of Chemistry, M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119992 Moscow, Russian Federation
f Department of Ecology and Soil Sciences, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan
*Corresponding authors
Phone: +351 218419237
E-mail addresses:
kamran_chem@mail.ru (Kamran T. Mahmudov)
pombeiro@tecnico.ulisboa.pt (Armando J. L. Pombeiro)
Organometallic and catalytic chemists from Portugal, Azerbaijan and Russia dedicate this work to
Professor Irina Petrovna Beletskaya.
Abstract
Two known organotin(IV) complexes, [Sn(C6H5)3HL1] (1, H2L1 = 2-(2-(2,4-dioxopentan-3-
ylidene)hydrazinyl)benzoic acid) and [Sn(C2H5)2(1κO,2κO-H3L2)(1κO2-H3L2)(µ3-O)]2 (2, H4L2 = 2-
(2-(2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)hydrazinyl)benzoic acid) were synthesized. Both
compounds 1 and 2 act as homogenous catalysts for the diastereoselective nitroaldol (Henry)
reaction of aliphatic and aromatic aldehydes with nitroethane in different solvents such as
dichloromethane, acetonitrile or methanol. Complex 2 was found to be the more efficient catalyst
for the Henry reaction in methanol, producing β-nitroalcohols with good yields (65−89 %) and
diastereoselectivities (syn/anti 72:28−77:23).
Keywords: Di- and triorganotin(IV) complexes; C−C coupling of aldehydes with nitroethane; β-
nitroalcohols.
1. Introduction
Due to the Lewis acid character of organotin compounds, they are an important class of acid
catalysts, which are milder than Brønsted acids, but their utilization has been significantly increased
[1−6]. For instance, organotin compounds are applied as homogeneous catalysts in a series of
industrial reactions, in which esters are produced via (trans)esterification, e.g., in the synthesis of
fatty acid alkyl esters [3], polyesters [4,5] and lactones [6]. As far as we know, only one organotin
compound, (n-Bu)3SnH, has been applied in nitroaldol (Henry) reaction [7a].
The nitroaldol (Henry) is a Lewis acid/base-catalyzed C−C coupling of an aldehyde and
nitroalkane, to produce corresponding β-nitroalkanol (Scheme 1) [7]. The resulting products, β-
nitroalkanols, are important and versatile intermediates in the synthesis of 2-amino alcohols,
nitroalkenes and α-nitroketones [7−12]. For the synthesis of β-nitroalkanols, alkali metal
hydroxides, alkoxides or amines [13,14], as well as heterobimetallic complexes with lanthanide

ACCEPTED MANUSCRIPT
BINOL (BINOL = 2,2'-dihydroxy-1,1'-binaphthyl) systems [15], Mg–Al hydrotalcite [16,17],
guanidines [18], benzyltrimethylammonium hydroxide [19], a rhodium complex in the presence of
a silyl ketene acetal [20], amberlyst A-21 [13], cinchona alkaloid [21], proazaphosphatranes [22],
Cu-bis(oxazoline) [23] or Co-salen (salen = N,N'-bis(salicylidine)ethylenediamine) complexes
[24,25] Zn(II) dinuclear complexes [26,27] or a mixture of Zn(OTf)2 (OTf = triflate) and (+)-N-
methylephedrine [28], Cu(II)-arylhydrazones [29], Zn(II)-1,3,5-triazapentadienato [30], etc. were
applied as homogeneous catalysts in Henry reaction between aldehydes and nitroalkanes. However,
there is no application of organotin complexes in this transformation. Thus, the search for efficient
and cheap homogenous protocol for the C−C coupling of aldehydes with nitroalkanes is still highly
desirable.
Scheme 1. The nitroaldol (Henry) reaction.
Hence, on the basis of the above considerations, we focused this work on the following
aims: i) to prepare known di- and triorganotin(IV) complexes, [Sn(C6H5)3HL1] (1, H2L1 = 2-(2-(2,4-
dioxopentan-3-ylidene)hydrazinyl)benzoic acid) and [Sn(C2H5)2(1κO,2κO-H3L2)(1κO2-H3L2)(µ3-
O)]2 (2, H4L2 = 2-(2-(2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene)hydrazinyl)benzoic acid)
(Scheme 2) [31]; ii) to test the catalytic activity of the prepared di- and triorganotin(IV) complexes
in nitroaldol reaction.
O
C
O
C
N
N
O
HN
C
NH
C
C
C
C
C
N
N
C2H5
Sn
C2H5
.
.
.
H
.
.
.
H
.
C
C
.
.
.
.
.
O
O
O
O
N
H
O
O
N
H
O
Sn
C
C2H5
C2H5
C2H5
O
Sn
Sn
C
O
C2H5
Sn
O
.
O
.
O
.
.
H3C
.
.
H
H
C
C
H
N
.
O
.
O
O
.
.
O .
N
.
N
O
O
O
O
.
.
.
.
.
.
C2H5
C2H5
C
C
C
H
N
C
H
C
O
N
C
N
C
C
HN
NH
N
N
C
O
C
O
CH3
2
1
Scheme 2. Schematic representations of complexes 1 and 2 [31].
2. Experimental
2.1. Materials and instrumentation
All the chemicals were obtained from commercial sources (Aldrich) and used as received. H2L1,
H4L2, 1 and 2 were synthesized according to the reported procedure [31]. The 1H NMR spectra were
recorded at room temperature on a Bruker Avance II + 400 (UltraShieldTM Magnet) spectrometer
2

ACCEPTED MANUSCRIPT
operating at 400 MHz for proton. The chemical shift is reported in ppm using tetramethylsilane as
the internal reference.
2.2. Catalytic activity studies
To a 10 mL vial were added the catalyst (1.0−6.0 mol%) and 2 mL solvent (CH2Cl2, MeCN or
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) [32]. The
analytical data of the obtained β-nitroalcohols are in good agreement with literature [33,34]. The
1
syn/anti diastereoselectivity of the β-nitroalcohols was determined by H NMR spectroscopy (in
CDCl3) based on the vicinal coupling constants of the products between the α-N−C−H and the α-
O−C−H [17,32−35].
3. Results and discussion
Firstly, we examined the catalytic performance of 1 and 2, as well as Ph3SnCl, (Et2Sn)O, H2L1 and
H4L2 in a model nitroaldol reaction between benzaldehyde and nitroethane in different solvents
(dichloromethane, acetonitrile and methanol) at room temperature (Table 1). The use of protic
solvents usually provides better results than aprotic ones [36−38], what is also observed in our case
(Table 1). Catalyst 2 behaves as the most active (73%) and diastereoselective (syn : anti = 74:26)
catalyst among Ph3SnCl, (Et2Sn)O, H2L1, H4L2, 1 and 2 in the methanol medium as well as under
catalyst- and solvent-free conditions (entry 28, Table 1). In methanol, the catalytic activity of
complex 2 is higher than that of 1 (entries 25 and 28, Table 1), what can eventually be associated to
the acidic protons of the pyrimidine moiety of the former complex, where the NH group(s) can play
a H-bond donor role in the activation of the C=O group of benzaldehyde. Thus, methanol was
chosen as the sole solvent for further studies. Control (blank) experiments were carried out in the
absence of any metal catalyst or in the presence of Ph3SnCl, (Et2Sn)O, H2L1 and H4L2. In the
former case (entries 2−4) no nitroaldol coupling product was detected, whereas, with Ph3SnCl,
(Et2Sn)O, H2L1 or H4L2 low product yield (7, 6, 2 or 7 %, respectively) was obtained (entries
11−22) in methanol. To establish the optimized conditions, the variations of reaction time (0.5−24
h), catalyst amount (1−6 mol %) and temperature (20−75oC) were applied (Table 2). The increase
of reaction time from 0.5 h to 24 h led to higher conversion (entries 1−6, Table 2), however the 6 h
appears to be the optimal reaction time. The variation (1−6 mol %) of the catalyst amount (entries
7−12) resulted in a significance effect on the yield. Thus, 5 mol % loading is optimal for the given
reaction conditions and thus this amount was used for the further studies. By increasing the
3

ACCEPTED MANUSCRIPT
temperature from 20oC to 75ºC the yield of the corresponding β-nitroalkanol was little more but
with lower diasteroselectivity (entries 11, 13−15, Table 2). Hence, room temperature was taken as
optimized temperature for this reaction giving good yield (78%) of corresponding β-nitroalkanol
with syn : anti = 74:26 (entry 11, Table 2).
Table 1. Catalyst screening and optimization.a
Entry
Catalyst
Blank
Solvent
No solvent
CH2Cl2
MeCN
MeOH
CH2Cl2
MeCN
MeOH
CH2Cl2
MeCN
MeOH
CH2Cl2
MeCN
MeOH
CH2Cl2
MeCN
MeOH
CH2Cl2
MeCN
MeOH
CH2Cl2
MeCN
MeOH
Yield, %c
Selectivity, syn/antid
1b
−
−
−
−
3
4
7
2
4
6
−
−
2
−
−
7
−
−
−
−
2
Blank
Ph3SnCl
(Et2Sn)O
H2L1
H4L2
1
3
4
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
55:45
56:44
58:42
56:44
53:47
50:50
−
−
51:49
−
−
53:47
61:39
66:34
70:30
68:32
70:30
74:26
32
46
59
39
57
73
2
a
Reaction conditions: catalyst precursor: Ph3SnCl, (Et2Sn)O, 1 and 2 (4.0 mol%), dichloromethane, acetonitrile or
o
b
d
methanol (2 mL), nitroethane (4 mmol) and benzaldehyde (1 mmol), reaction time: 24h, reaction temperature: 20 C.
c
Solvent-free conditions, using nitroethane as solvent (2 mL), Isolated yields after column chromatography.
Determined by 1H NMR.
Table 2. Optimization of the Henry reaction condition catalyzed by 2.a
Entry Time, h Amount of catalyst, mol%
Temp., ºC
Yield, %b
Selectivity, syn/antic
1
2
3
4
5
6
0.5
1
4
6
8
4.0
4.0
4.0
4.0
4.0
4.0
20
20
20
20
20
20
33
49
67
73
73
73
74:26
74:26
75:25
75:25
74:26
74:26
24
7
8
9
10
11
12
6
6
6
6
6
6
1.0
2.0
3.0
4.0
5.0
6.0
20
20
20
20
20
20
29
50
65
73
78
78
75:25
75:25
74:26
74:26
74:26
75:25
13
14
15
6
6
6
5.0
5.0
5.0
35
55
75
80
82
83
73:27
72:28
70:30
16d
6
5.0
20
36
70:30
a Reaction conditions: 1.0−6.0 mol% of catalyst precursor (typically 5.0 mol%), MeOH (2 mL), nitroethane
(4 mmol) and aldehyde (1 mmol). b Isolated yields after column chromatography. c Determined by 1H NMR.
d Solvent-free conditions, using nitroethane as solvent (2 mL).
4

ACCEPTED MANUSCRIPT
The substrate scope was then investigated. A variety of aliphatic and aromatic aldehydes
were tested under the optimized conditions using 2 as the catalyst (Table 3). As shown in Table 3,
β-nitroalcohols are obtained in moderate to good yields ranging from 65% to 89%. Aldehydes
containing either electron-donating or electron-withdrawing substituents at para- position of the
aromatic ring of aryl aldehydes gave moderate yields (69−85%) with similar diasteroelectivities
(entries 1−7, Table 3). In general, the electron-withdrawing substituents on the phenyl ring of the
aryl aldehydes favour the reaction, whereas electron-donating ones decrease the yield of β-
nitroalcohols. When the reaction was performed with 2-methylbenzaldehyde and 2,4,6-
trimethylbenzaldehyde, the corresponding 2-nitroalcohols were obtained in 67% and 65% yields
with similar diasteroelectivities, which shows that the position of substituents were hampered the
reaction (compare the entries 3, 8 and 9 in Table 3). Furthermore, aliphatic aldehydes were
smoothly converted to β-nitroalcohols in good yields and diasteroelectivity (up to syn/anti = 77:23)
(entries 10−14, Table 3).
Table 3. Henry reaction of nitroethane with various aldehydes catalyzed by 2.a
Entry
1
Substrate
Yield, % b
69
Selectivity, syn/antic
73:27
2
3
4
5
6
7
73
74
78
79
80
85
73:27
74:26
74:26
74:26
75:25
75:25
8
9
67
65
73:27
72:28
CH3CH2CHO
CH3(CH2)2CHO
CH3(CH2)3CHO
CH3(CH2)4CHO
CH3(CH2)5CHO
10
11
12
13
14
89
88
88
87
85
77:23
77:23
77:23
76:24
76:24
a
Reaction conditions: 5.0 mol% of catalyst 2, MeOH (2 mL), nitroethane (4 mmol) and aldehyde (1 mmol), reaction
time: 6 h. b Isolated yields after column chromatography. c Determined by 1H NMR.
5

ACCEPTED MANUSCRIPT
The activity of 2 is much higher than those reported for other metal catalysts: the
scorpionate complex [NiCl{SO3C(pzPh)3}] (pz = pyrazolyl; 31.5% yield for benzadehyde) [39],
lanthanide/sodium amide systems (48−85%) [15], pyrrolidine-based organocatalyst (67%) [40],
copper(II) complexes (70–77%) with amidoterephthalate [41], 2-((E)-(((1S)-quinolin-4-yl(5-
vinylquinuclidin-2-yl)methyl)imino) methyl)phenol (72) [42], (S)-2-((2-(hydroxydiphenylmethyl)
pyrrolidin-1-yl)methyl)-6-(trifluoromethyl) phenol (81) [43], etc.
The reaction mechanism should be similar to the reported examples with related catalytic
system [29]: ligand-assisted (with free C=O group, as a H-bond acceptor) deprotonation of the
methylene group of nitroethane (to give a nitronate species), and then an activation of benzaldehyde
by cooperation of metal center and free NH moieties of 2 towards an electrophilic attack occurs.
Finally, the attack on the nitronate leads to the respective C−C coupling to give a β-nitroalkanol
product.
4. Conclusions
Two previously reported di- and triorganotin(IV) complexes bearing arylhydrazones of active
methylene compounds [31] have been prepared and applied as catalysts in the C−C coupling of
aldehydes with nitroethane (Henry reaction). Due to the acidic proton(s) of the pyrimidine moiety,
the catalytic activity of complex 2 (diorganotin) is higher than that of 1 (triorganotin) in methanol at
room temperature, providing β-nitroalkanols in high yields (65−89%) in 6 h. To our knowledge
current study is the first report on the application of Sn(IV)-arylhydrazone complexes in Henry
reaction, and thus it opens such a possibility and shows that complexes of that type can operate
effectively in the presence of protic solvent methanol. Further modifications of the arylhydrazone
ligands deserve to be explored to reach a higher diasteroselectivity and yield.
Acknowledgements
Authors are grateful to the Fundação para a Ciência e a Tecnologia (FCT) (project
UID/QUI/00100/2013), Portugal, for financial support. This work also was supported by 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.
References
[1]
[2]
M.R. Meneghetti, S.M.P. Meneghetti, Catal. Sci. Technol. 5 (2015) 765.
T. Weidlich, L. Dušek, B. Vystrčilová, A. Eisner, P. Švec, A. Růžička, Appl. Organometal.
Chem. 26 (2012) 293.
[3]
Y.C. Brito, D.A.C. Ferreira, D.M.A. Fragoso, P.R. Mendes, C.M.J. de Oliveira, M.R.
Meneghetti, S.M.P. Meneghetti, Appl. Catal. A 443 (2012) 202.
6

ACCEPTED MANUSCRIPT
[4]
G. Deshayes, F.A.G. Mercier, P. Degee, I. Verbruggen, M. Biesemans, R. Willem, P.
Dubois, Chem. Eur. J. 9 (2003) 4346.
[5]
[6]
[7]
S. Shyamroy, B. Garnaik, S. Sivaram, J. Polym. Sci., Part A: Polym. Chem. 43 (2005) 2164.
I. Shiina, Chem. Rev. 107 (2007) 239.
a) S. Chandrasekhar, A. Shrinidhi, Synthetic Commun. 44 (2014) 3008; b) M. Shibasaki, M.
Kanai, S. Matsunaga, N. Kumagai, Multimetallic multifunctional catalysts for asymmetric
reactions: bifunctional molecular catalysis, in: T. Ikariya, M. Shibasaki (Eds.), Topics in
Organometallic Chemistry, 37, Springer-Verlag, Berlin/Heidelberg, 2011, p. 1; c) S.K.
Ginotra, V.K. Singh, Org. Biomol. Chem. 5 (2007) 3932; d) J.D. White, S. Shaw, Org.
Lett. 14 (2012) 6270; e) B. Yi, Y. Yin, Z. Yi, W. Zhou, H. Liu, N. Tan, H. Yang,
Tetrahedron Lett. 57 (2016) 2320; f) Y. Zhang, B.-W. Wei, L.-N. Zou, M.-L. Kang, H.-Q.
Luo, X.-L. Fan, Tetrahedron 72 (2016) 2472; g) N. Surneni, N.C. Barua, B. Saikia,
Tetrahedron Lett. 57 (2016) 2814; h) L. Harmand, P. Drabina, V. Pejchal, L. Husáková, M.
Sedlák, Tetrahedron Lett. 56 (2015) 6240; i) H. Cruz, G. Aguirre, D. Madrigal, D. Chávez,
R. Somanathan, Tetrahedron: Asymm. 27 (2016) 1217; j) G. Lu, F. Zheng, L. Wang, Y.
Guo, X. Li, X. Cao, C. Wang, H. Chi, Y. Dong, Z. Zhang, Tetrahedron: Asymm. 27 (2016)
732; k) J.-L. Li, L. Liu, Y.-N. Pei, H.-J. Zhu, Tetrahedron 70 (2014) 9077; l) H. Naïli, F.
Hajlaoui, T. Mhiri, T. C. O. Mac Leod, M.N. Kopylovich, K.T. Mahmudov, A. J. L.
Pombeiro, Dalton Trans. 42 (2013) 399; m) E. Wolińska, Tetrahedron 69 (2013) 7269; n) B.
Ni, J. He, Tetrahedron Lett. 54 (2013) 462; o) N. Neelakandeswari, G. Sangami, P.
Emayavaramban, R. Karvembu, N. Dharmaraj, H.Y. Kim, Tetrahedron Lett. 53 (2012)
2980; p) A. Das, M.K. Choudhary, R.I. Kureshy, K. Jana, S. Verma, N.H. Khan, S.H.R.
Abdi, H.C. Bajaj, B. Ganguly, Tetrahedron 71 (2015) 5229; q) K.T. Mahmudov, M. F. C.
Guedes da Silva, M. Sutradhar, M. N. Kopylovich, F. E. Huseynov, N. T. Shamilov, A. A.
Voronina, T. M. Buslaeva, A. J. L. Pombeiro, Dalton Trans. 44 (2015) 5602.
[8]
[9]
G. Rosini, B.M. Trost (Eds.), In Comprehensive Organic Synthesis, vol. 2,
Pergamon, New York, 1991, pp. 321–340.
K. Iseki, S. Oishi, H. Sasai, M. Shibasaki, Tetrahedron Lett. 37 (1996) 9081.
[10] A. Barco, S. Benetti, C. Risi, G. Polloni, Tetrahedron Lett. 37 (1996) 7599.
[11] H. Sasai, M. Hiroi, Y. Yamada, M. Shibasaki, Tetrahedron Lett. 38 (1997) 6031.
[12] M. Shibasaki, H. Sasai, T. Arai, Angew. Chem., Int. Ed. Engl. 36 (1997) 1236.
[13] R. Ballini, G. Bosica, P. Forconi, Tetrahedron 52 (1996) 1677.
[14] G. Rosini, R. Ballini, Synthesis (1988) 833.
[15] T. Nitabaru, N. Kumagai, M. Shibasaki, Tetrahedron Lett. 49 (2008) 272.
[16] B. M. Choudary, M. L. Kantam, B. J. Kavita, Mol. Catal. A Chem. 169 (2001) 193.
[17] A. Cwik, A. Fuchs, Z. Hella, J. Clacens, Tetrahedron 61 (2005) 4015.
[18] R. Chinchilla, C. Najera, P. Sánchez-Agulló, Tetrahedron Asymm. 5 (1994) 1393.
[19] V.J. Bulbule, G.K. Jnaneshwara, R.R. Deshmukh, H.B. Borate, V.H. Deshpande, Synth.
Commun. 31 (2001) 3623.
[20] S. Kiyooka, T. Tsutsui, H. Maeda, Y. Kanelo, K. lsobe, Tetrahedron Lett. 36 (1995) 6531.
[21] E.J. Corey, F.Y. Zhang, Angew. Chem., Int. Ed. 38 (1999) 1931.
[22] P.B. Kisanga, J.G. Verkade, J. Org. Chem. 64 (1999) 4298.
[23] T. Risgaard, K.V. Gothelf, K.A. Jørgensen, Org. Biomol. Chem. 1 (2003) 153.
[24] T. Yamada, Synthesis-Stuttgart 12 (2004) 1947.
7

ACCEPTED MANUSCRIPT
[25] Y. Kogami, T. Nakajima, T. Ashizawa, S. Kezuka, T. Ikeno, T. Yamada, Chem. Lett. 33
(2004) 614.
[26] B.M. Trost, V.S.C. Yeh, Angew. Chem., Int. Ed. 41 (2002) 861.
[27] B.M. Trost, V.S.C. Yeh, H. Ito, N. Bremeyer, Org. Lett. 4 (2002) 2621.
[28] C. Palomo, M. Oiarbide, A. Laso, Angew. Chem., Int. Ed. 44 (2005) 3881.
[29] Z. Ma, A.V. Gurbanov, A.M. Maharramov, F.I. Guseinov, M.N. Kopylovich, F.I. Zubkov,
K.T. Mahmudov, A.J.L. Pombeiro, J. Mol. Cat. A Chem. 426 (2017) 526.
[30] N.Q. Shixaliyev, A.M. Maharramov, A.V. Gurbanov, V.G. Nenajdenko, V.M.
Muzalevskiy, K.T. Mahmudov, M.N. Kopylovich, Catalysis Today 217 (2013) 76.
[31] K.T. Mahmudov, M.F.C. Guedes da Silva, A. Mizar, M.N. Kopylovich, A.R. Fernandes, A.
Silva, A.J.L. Pombeiro, J. Organomet. Chem. 760 (2014) 67.
[32] M. Solinas, B. Sechi, S. Baldino, G. Chelucci, J. Mol. Cat. A: Chem. 378 (2013) 206.
[33] W. Jin, X. Li, B. Wan, J. Org. Chem. 76 (2011) 484.
[34] G. Blay, L.R. Domingo, V. Hernández-Olmos, J.R. Pedro, Chem. Eur. J. 14 (2008) 4725.
[35] V.J. Bulbule, V.H. Deshpande, S. Velu, A. Sudalai, S. Sivasankar, V.T. Sathe, Tetrahedron
55 (1999) 9325.
[36] A.G. Doyle, E.N. Jacobsen, Chem. Rev. 107 (2007) 5713.
[37] F. Lopez, A.J. Minnaard, B.L. Feringa, Acc. Chem. Res. 40 (2007) 179.
[38] Y. Jung, R.A. Marcus, J. Am. Chem. Soc. 129 (2007) 5492.
[39] B.G.M. Rocha, T.C.O. Mac Leod, M.F.C. Guedes da Silva, K.V. Luzyanin, L.M.D.R.S.
Martins, A.J.L. Pombeiro, Dalton Trans. 43 (2014) 15192.
[40] P. Chintala, S.K. Ghosh, E. Long, A.D. Headley, B. Nia, Adv. Synth. Catal. 353 (2011)
2905.
[41] A. Karmakar, S. Hazra, M.F.C. Guedes da Silva, A.J.L. Pombeiro, New J. Chem. 38 (2014)
4837.
[42] Y. Wei, L. Yao, B. Zhang, W. He, S. Zhang, Tetrahedron 67 (2011) 8552.
[43] K. Xu, G. Lai, Z. Zha, S. Pan, H. Chen, Z. Wang, Chem. Eur. J. 18 (2012) 12357.
8

ACCEPTED MANUSCRIPT
Highlights
► Arylhydrazone diorganotin(IV) complex acts as an effective catalyst in the nitroaldol reaction
► The β-nitroalcohols were obtained in good to high yield
► The activity depends on the amounts of catalyst and nature of solvents