Cyanosilylation of aldehydes catalyzed by lanthanide derivatives comprising arylhydrazones of β-diketones

Article abstract of DOI:10.1016/j.jorganchem.2017.08.013

Two known lanthanide complexes, [KLa(HL¹)₂{(CH₃)₂NCHO}₂(H₂O)₃] (1) and [Sm(H₂O)₉](E-H₂L²)₃·2H₂O (2) were prepare

Full text of DOI:10.1016/j.jorganchem.2017.08.013

Accepted Manuscript
Cyanosilylation of aldehydes catalyzed by lanthanide derivatives comprising
arylhydrazones of β-diketones
Fatali E. Huseynov, Nazim T. Shamilov, Kamran T. Mahmudov, Abel M. Maharramov,
M.Fátima C. Guedes da Silva, Armando J.L. Pombeiro
PII:
S0022-328X(17)30502-8
10.1016/j.jorganchem.2017.08.013
JOM 20066
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 13 August 2017
Revised Date: 21 August 2017
Accepted Date: 22 August 2017
Please cite this article as: F.E. Huseynov, N.T. Shamilov, K.T. Mahmudov, A.M. Maharramov, M.Fá.C.
Guedes da Silva, A.J.L. Pombeiro, Cyanosilylation of aldehydes catalyzed by lanthanide derivatives
comprising arylhydrazones of β-diketones, Journal of Organometallic Chemistry (2017), doi: 10.1016/
j.jorganchem.2017.08.013.
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Graphical Abstract

ACCEPTED MANUSCRIPT
Cyanosilylation of aldehydes catalyzed by lanthanide
derivatives comprising arylhydrazones of β-diketones
Fatali E. Huseynov,a,b Nazim T. Shamilov, a,b Kamran T. Mahmudov,a,b,c,*
Abel M. Maharramov,d M. Fátima C. Guedes da Silva,c Armando J. L. Pombeiroc,
*
a Department of Ecology and Soil Sciences, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan
b Organic Chemistry Department, RUDN University, 6 Miklukho-Maklaya str., Moscow 117198, Russian Federation
c Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–001
Lisbon, Portugal
d Organic Chemistry Department, 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)
This paper is dedicated to Prof. Irina. P. Beletskaya, well-known expert in organometallic
chemistry and catalysis.
Abstract
Two known lanthanide complexes, [KLa(HL1)2{(CH3)2NCHO}2(H2O)3] (1) and [Sm(H2O)9](E-
H2L2)3·2H2O (2) were prepared by reaction of lanthanum(III) and samarium(III) nitrates with
potassium
3-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)-2-hydroxy-5-nitrobenzenesulfonate
(KH2L1) and potassium (E,Z)-5-chloro-3-(2-(1,3-dioxo-1-phenylbutan-2-ylidene)hydrazinyl)-2-
hydroxybenzenesulfonate (KH2L2), respectively. Catalytic activities of 1 and 2 were evaluated in
the cyanosilylation of aldehydes with trimethylsilyl cyanide in different solvents such as
tetrahydrofuran, dichloromethane or methanol. Complex 1 was found to be efficient catalyst for the
cyanosilylation reaction in methanol medium at room temperature, producing cyanohydrin
trimethylsilyl ethers with good yields (76−99 %).
Keywords: Lanthanide complexes, arylhydrazones of β-diketones; catalysis; cyanosilylation of
aldehydes.
1. Introduction
Cyanosilylation of aldehydes is an efficient method for the synthesis of silylated cyanohydrins
(Scheme 1), which are readily transformed into many valuable chemicals with functional groups
including α-hydroxy carbonyl compounds, β-amino alcohols and other building blocks [1−10]. To
date, heterogeneous catalysts reported for the cyanosilylation reactions are dominated in
comparison to homogeneous ones. Owing to the increasing environmental problems, current
interest is focused on the development of environmentally friendly catalysts for clean processes in
the fine chemical industry. Hence, various types of catalysts, N-methylmorpholine N-oxide [11],
1,1,3,3-tetramethylguanidine [12], N-heterocyclic carbenes [13,14], P(RNCH2CH2)N [15],
tetraethylammonium 2-(N-hydroxycarbamoyl)benzoate [16], Yb(OTf)3 [17,18], Yb(CN)3 [19], ZnI2
[20], Cu(OTf)2 [21], KCN:18-crown-6 [22], R2SnCl2 an Sn-montmorillonite [23,24], LiCl and
LiClO4 [25−27], CsF [28,29], MgBr2·Et2O [30], Zr(KPO4)2 [31], VO(OTf)2 [32], NbF5 [33], InBr3

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[34], FeCl3 [35], Fe(Cp)2PF6 [36], lead(II)-3-aminopyrazine-2-carboxylate [37], Cu(II)-hydrazone
complexes [38−40], lanthanide-containing polyoxometalates intercalated layered doublehydroxides
[41], supported ionic liquid [42], metal organic frameworks (MOF's) [43−48], arylhydrazone di-
and triorganotin(IV) complexes [49], etc. were applied for cyanosilylation of aldehydes. It should
be note that early work on cyanohydrin synthesis was carried out with hydrogen cyanide as the
cyanide source [2]. The volatility and extreme toxicity of this reagent causes obvious difficulties
and ecological problems, and numerous alternative cyanide-based reagents such as trimethylsilyl
cyanide (TMSCN), NaCN, KCN, etc. have since been developed [1,2]. But, TMSCN is safe and
easy to handle source of cyanide compared to other mentioned ones.
We herein report the use of the known lanthanide complexes 1 and 2 (Scheme 2) [50],
obtained by reaction of lanthanide nitrates with arylhydrazones of β-diketones, as the homogenous
catalysts for the cyanosilylation of aliphatic and aromatic aldehydes with trimethylsilyl cyanide
(TMSCN) to afford cyanohydrin trimethylsilyl ethers in high yields at room temperature (Scheme
1).
Scheme 1. Cyanosilylation of aldehydes.
Scheme 2. Schematic representations of 1 and 2 [50].
2. Experimental
2.1. Materials and instrumentation
All the chemicals were obtained from commercial sources (Aldrich) and used as received. KH2L1,
1
KH2L2, 1 and 2 were synthesized according to the reported procedure [50]. The H NMR spectra
were recorded at room temperature on a Bruker Avance II + 300 (UltraShieldTM Magnet)
spectrometer operating at 300.130 MHz for proton. The chemical shift is reported in ppm using
tetramethylsilane as the internal reference.
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2.2. Catalytic activity studies
The solvent (THF, CH2Cl2 or anhydrous MeOH; 2 mL) was added to a flask which contained the
catalyst (1 or 2) (1–10 mol%) and aldehyde (0.4 mmol), the solution was stirred continuously and
the progress of the reaction was followed by TLC. The crude reaction mixture was characterized by
1H-NMR. The yield of the products was determined by 1H-NMR [38−40,49,51−53]. The adequacy
1
of the procedure was confirmed by blank H NMR analyses with 1,2-dimethoxyethane as an
internal reference. The internal standard method proved that no side products were formed.
3. Results and discussion
The addition reactions of TMSCN to benzaldehyde (Scheme 1) were carried out in order to
compare the catalytic performance of the 1, 2, KH2L1, KH2L2, La(NO3)3·6H2O and
Sm(NO3)3·6H2O in protic (methanol) and aprotic (1,2-dichloromethane and THF) solvents (Table
1). As can be seen, methanol is the most appropriate solvent (entries 1−14), presumably due to the
high solubility of 1 and 2 in this solvent. KH2L1, KH2L2, La(NO3)3·6H2O and Sm(NO3)3·6H2O lead
to the yield of cyanohydrin trimethylsilyl ethers of 29−50 % in 16 h (entries 11−14), what is
substantially lower than those obtained in the presence of complexes 1 and 2 (79 and 88 %, entries
5 and 6) in methanol. The catalytic activity of complex 1 is higher than that of 2 (entries 5 and 6),
what can eventually be associated to the basic character of this compound. Low yield of
cyanohydrin trimethylsilyl ethers were obtained in the absence of catalysts, as well as under
solvent-free conditions (entries 15−20).
Table 1. Selection of catalyst for the cyanosilylation of benzaldehyde with TMSCN.a
Entry
1
2
3
4
5
6
7
8
Catalyst
Time (h)
16
Amount of catalyst (mol%)
Solvent
THF
THF
CH2Cl2
CH2Cl2
MeOH
MeOH
THF
Yieldb (%)
50.2
64.5
57.5
68.6
87.7
79.5
14.2
14.8
18.4
18.6
30.3
29.1
49.6
50.2
17.1
45.0
14.0
22.3
13.0
20.0
3
3
3
3
3
3
3
3
3
3
3
3
3
3
-
1
2
1
2
1
2
16
16
16
16
16
16
16
16
16
16
16
16
16
48
6 days
24
16
KH2L1
KH2L2
THF
9
KH2L1
CH2Cl2
CH2Cl2
MeOH
MeOH
MeOH
MeOH
CH2Cl2
CH2Cl2
THF
10
11
12
13
14
15c
16c
17c
18c
19c
20c
KH2L2
KH2L1
KH2L2
La(NO3)3·6H2O
Sm(NO3)3·6H2O
-
-
-
-
-
-
-
-
-
-
MeOH
-
16
24
-
-
a
Reaction conditions: solvent (2 mL), TMSCN (0.6 mmol) and aldehyde (0.4 mmol), in air at room temperature.
b Determined by 1H NMR analysis of crude products. c Adapted from reference [49].
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As 1 was found to be the most active catalyst among the 1, 2, KH2L1, KH2L2,
La(NO3)3·6H2O and Sm(NO3)3·6H2O and methanol was the most appropriate solvent, we
furthermore studied different effects using 1 as a catalyst and methanol as a solvent. As can be seen
(Table 2, entries 1−4), the reaction was completed after 2 h, and the variation of the catalyst amount
(entries 5−9) allowed to conclude that 4 mol % loading is optimal for the given reaction conditions
and thus this amount was used for the further studies. The temperature also has not crucial effect on
the yields of cyanohydrin trimethylsilyl ethers (entries 10−14).
Table 2. Evaluation of reaction conditions of cyanosilylation of benzaldehyde with TMSCN
catalyzed by 1.a
Entry
Time (h)
Amount of catalyst, (mol%)
T (˚C)
25
25
25
25
Yieldb (%)
79.3
1
2
3
4
0.5
1
2
3
3
3
3
84.5
87.6
87.7
3
5
6
7
8
9
2
2
2
2
2
1
2
3
4
5
25
25
25
25
25
57.5
77.3
87.7
89.8
89.9
10
11
12
13
14
2
2
2
2
2
4
4
4
4
4
15
35
25
45
55
84.4
90.1
89.8
91.4
92.9
a Reaction conditions: MeOH (2 mL), TMSCN (0.6 mmol) and benzaldehyde (0.4 mmol), in air.
b Determined by 1H NMR analysis of crude products (see Experimental part).
The substrate scope of asymmetric cyanosilylation was investigated under optimized
conditions using 1 as a catalyst (Table 3). Both aliphatic and aromatic aldehydes are well tolerated
with this reaction protocol and could be converted to the corresponding cyanohydrin trimethylsilyl
ethers in good yields. Aliphatic aldehydes and benzaldehydes bearing para- electron-withdrawing
groups on aromatic rings proceed smoothly to give the respective cyanosilylation products with
high yields (entries 1−8). Benzaldehydes bearing para- electron-donating groups (entries 10−12,
Table 3) react much more slowly than benzaldehydes with electron-withdrawing groups. This
tendency is explained by the higher electropositive charge on the carbonyl group of aldehyde
achieved in the presence of electron-withdrawing groups, resulting in a higher activation of the
substrate [54]. In contrast, for the electron-donating group, the activation of the carbonyl group is
lower.
The use of 1 as a catalyst has several advantages in comparison to the other reported
homogeneous systems. For instance, a Zn(II) system provided low yield (30%) and required a low
temperature (0 oC) [55], a Ti(IV) system required a long reaction time (48 h) and low temperature (-
4

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o
20 C) [56], a Cu(II) system also provided a low yield (27%), long reaction time (48 h) and high
temperature (40o C) [57], and an Al(III) one required a long reaction time (18 or 96 h) and a low
temperature of -50 or -40 oC [58,59].
Table 3. Addition of TMSCN to various aldehydes catalysed by catalyst 1 in methanol.a
Entry
Substrate
Yieldb (%)
99.5
1
2
3
4
5
6
CH3CH2CHO
CH3(CH2)2CHO
CH3(CH2)3CHO
CH3(CH2)4CHO
CH3(CH2)5CHO
99.3
99.0
98.7
97.9
94.4
90.7
7
8
90.5
89.8
84.8
83.7
76.2
9
10
11
12
a
Reaction conditions: 4 mol% of catalyst 1, MeOH (2 mL), TMSCN (0.6 mmol) and aldehyde (0.4 mmol). Reaction
time: 2 h. b Determined by 1H NMR analysis of crude products.
4. Conclusions
Two previously reported lanthanide complexes, [KLa(HL1)2{(CH3)2NCHO}2(H2O)3] (1) and
[Sm(H2O)9](E-H2L2)3·2H2O (2) [50] catalyze the cyanosilylation reaction between trimethylsilyl
cyanide and both aliphatic and aryl aldehydes, providing in an efficient and simple method the
desired cyanohydrin trimethylsilyl ethers in good to excellent yields (up to 99%) in methanol at
room temperature. Due to the basic character of 1, the catalytic activity of this complex is higher
than that of 2. In comparison to reported methods [55−59], there are several advantages in the use
of 1 as a catalyst in this reaction: i) it is easily available from cheap starting materials (lanthanide
nitrate and arylhydrazone of β-diketone); ii) both aromatic and aliphatic aldehydes are employed
effectively; iii) a high product yield is achieved in methanol medium and at room temperature.
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 was also supported by the
Ministry of Education and Science of the Russian Federation (Agreement number 02.a03.21.0008).
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References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
N. Kurono, T. Ohkuma, ACS Catal. 6 (2016) 989.
M. North, D.L. Usanov, C. Young, Chem. Rev. 108 (2008) 5146.
J. Gawronski, N. Wascinska, J. Gajewy, Chem. Rev. 108 (2008) 5227.
J. Holt, U. Hanefeld, Curr. Org. Synth. 6 (2009) 15.
M. Sakulsombat, P. Vongvilai, O. Ramstrom, Org. Biomol. Chem. 9 (2011) 1112.
C.Y. Chu, C.T. Hsu, P. H. Lo, B.J. Uang, Tetrahedron Asymm. 2 (2011) 1981.
M.G. Dekamin, Z. Mokhtari, Tetrahedron 68 (2012) 922.
S. Matsukawa, S. Fujikawa, Tetrahedron Lett. 53 (2012) 1075.
G.D. Yadav, M.S. Chauhan, S. Singh, Synthesis (2014) 629.
[10] S. Zhao, Y. Chen, Y.F. Song, Appl. Catal. A Gen. 475 (2014) 140.
[11] S.S. Kim, D.W. Kim, G. Rajgopal, Synthesis (2004) 213.
[12] L. Wang, X. Huang, J. Jiang, X. Liu, X. Feng Tetrahedron Lett. 47 (2006) 1581.
[13] J.J. Song, F. Gallou, J.T. Reeves, Z. Tan, N.K. Yee, C.H. Senanayake, J. Org. Chem. 71
(2006) 1273.
[14] Y. Suzuki, M.D. Abu Baker, K. Muramatsu, M. Sato, Tetrahedron 62 (2006) 4227.
[15] B.M. Fetterly, J.G. Verkade, Tetrahedron Lett. 46 (2005) 8061.
[16] M.G. Dekamin, Z. Karimi, M. Farahmand, Catal. Sci. Technol. 2 (2012) 1375.
[17] Y. Yang, D. Wang, Synlett (1997) 861.
[18] Y. Yang, D. Wang, Synlett (1997) 1379.
[19] S. Matsubara, T. Takai, K. Utimoto, Chem. Lett. (1991) 1447.
[20] P. G. Gassman, J. J. Talley, Tetrahedron Lett. 19 (1978) 3773.
[21] P. Saravanan, R.V. Anand, V. R. Singh, Tetrahedron Lett. 39 (1998) 3823.
[22] W.J. Greenlee, D.G. Hangauer, Tetrahedron Lett. 24 (1983) 4559.
[23] J.K. Whitesell, R. Apodaca, Tetrahedron Lett. 37 (1996) 2525.
[24] J. Wang, Y. Masui, K. Watanabe, M. Onaka, Adv. Synth. Catal. 351 (2009) 553.
[25] N. Kurono, M. Yamaguchi, K. Suzuki, T. Ohkuma, J. Org. Chem. 70 (2005) 6530.
[26] G. Jenner, Tetrahedron Lett. 40 (1999) 491.
[27] N. Azizi, M.R. Saidi, J. Organomet. Chem. 688 (2003) 283.
[28] S.S. Kim, D.H.O. Song, Lett. Org. Chem. (2004) 1264.
[29] S.S. Kim, G. Rajagopal, D.H.O. Song, J. Organomet. Chem. 68 (2004) 91734.
[30] D.E. Ward, M.J. Hrapchak, M. Sales, Org. Lett. 2 (2000) 57.
[31] M. Curini, F. Epifanio, M.C. Marcotullio, O. Rosati, M. Rossi, Synlett (1999) 315.
[32] K.D. Surya, A.G. Richard, J. Mol. Catal. A: Chem. 232 (2005) 123.
[33] S.S. Kim, G. Rajgopal, Synthesis (2007) 215.
[34] M. Bandini, P. G. Cozzi, A. Garelli, P. Melchiorre, A. U. Ronchi, Eur. J. Org. Chem. (2002)
3243.
[35] K. Iwanami, M. Aoyagi, T. Oriyama, Tetrahedron Lett. 46 (2005) 7487.
[36] N.H. Khan, S. Agrawal, R.I. Kureshy, S.H.R. Abdi, S. Singh, R.V. Jasra, J. Organomet.
Chem. 692 (2007) 4361.
[37] A. Karmakar, S. Hazra, M.F.C. Guedes da Silva, A.J.L. Pombeiro, Dalton Trans. 44 (2015)
268.
[38] A.G. Mahmoud, K.T. Mahmudov, M.F.C. Guedes da Silva, A.J.L. Pombeiro, RSC
Advances 6 (2016) 54263.
[39] 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. 428 (2017) 17.
[40] A.V. Gurbanov, K.T. Mahmudov, M. Sutradhar, M.F.C. Guedes da Silva, T.A. Mahmudov,
F.I. Guseinov, F.I. Zubkov, A.M. Maharramov, A.J.L. Pombeiro, J. Organomet. Chem. 834
(2017) 22.
[41] Y. Jia, S. Zhao, Y-F. Song, Applied Catalysis A: General 487 (2014) 172.
[42] S. Martin, R. Porcar, E. Peris, M. I. Burguete, E. G.Verdugo, S. V. Luis, Green Chem., 16
(2014) 1639.
6

ACCEPTED MANUSCRIPT
[43] P.K. Batista, D.J.M. Alves, M.O. Rodrigues, G.F. DeSá, S.A. Junior, J.A. Vale, J. Mol.
Catal A: Chem. 379 (2013) 68.
[44] L. Liu, Z.-B. Han, S.-M. Wang, D.-Q. Yuan, S.W. Ng, Inorg. Chem. 54 (2015) 3719.
[45] X. Cui, M.C. Xu, L.J. Zhang, R.X. Yao, X.M. Zhang, Dalton Trans. 44 (2015) 12711.
[46] X.M. Zhang, C.W. Zhao, J.P. Ma, Y. Yu, Q-K. Liu, Y.B. Dong, Chem. Commun. 51 (2015)
839.
[47] X. M. Lin, J.L. Niu, P.X. Wen, Y. Pang, L. Hu, Y.P. Cai, Cryst. Growth Des. 16 (2016)
4705.
[48] A. Karmakar, G.M.D.M. Rúbio, A. Paul, M.F.C. Guedes da Silva, K.T. Mahmudov, F.I.
Guseinov, S.A.C. Carabineiro, A.J.L. Pombeiro, Dalton Trans. 46 (2017) 8649.
[49] A.V. Gurbanov, F.E. Huseynov, A.M. Maharramov, M.F.C. Guedes da Silva, A.J.L.
Pombeiro, J. Organomet. Chem. 848 (2017) 118.
[50] 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.
[51] M. North, M. Omedes-Pujol, Beilstein J. Org. Chem. 6 (2010) 1043.
[52] Z. Zhang, J. Chen, Z. Bao, G. Chang, H.Xing, Q. Ren, RSC Adv. 5 (2015) 79355.
[53] G. Rajagopal, S. Selvaraj, K. Dhahagani, Tetrahedron: Asymm. 21 (2010) 2265.
[54] A. Bhunia, S. Dey, J.M. Moreno, U. Diaz, P. Concepcion, K.V. Hecke, C. Janiak, P.V.D.
Voort, Chem. Commun. 52 (2016) 1401.
[55] S. Neogi, M.K. Sharma, P.K. Bharadwaj, J. Mol. Cat. A Chem. 299 (2009) 1.
[56] E. Błocka, M.J. Bosiak, M. Wełniak, A. Ludwiczak, A. Wojtczak, Tetrahedron: Asymm. 25
(2014) 554.
[57] W.W. Lestari, P. Lönnecke, H.C. Streit, F. Schleife, C. Wickleder, E. Hey-Hawkins, Inorg.
Chim. Acta 421 (2014) 392.
[58] S.S. Kim, Pure Appl. Chem. 78 (2006) 977.
[59] Y. Hamashima, D. Sawada, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 121 (1999) 2641.
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Highlights
► Two known La-K and Sm complexes with arylhydrazones of β-diketones were prepared
► Catalytic activity of a heterometallic La-K complex is high in homogeneous cyanosilylation of
aldehydes
► High yield of cyanohydrin trimethylsilyl ethers is found in methanol at room temperature