Cyanosilylation of aldehydes catalyzed by arylhydrazone di- and triorganotin(IV) complexes

Article abstract of DOI:10.1016/j.jorganchem.2017.07.030

Two known organotin(IV) complexes, [Sn(C₆H₅)₃HL¹] (1) and [Sn(C₂H₅)₂(1κO,2κO-H₃L²) (1κO²-H₃L²) (μ₃-O)]₂

Full text of DOI:10.1016/j.jorganchem.2017.07.030

Accepted Manuscript
Cyanosilylation of aldehydes catalyzed by arylhydrazone di- and triorganotin(IV)
complexes
Atash V. Gurbanov, Fatali E. Huseynov, Abel M. Maharramov, M. Fátima C. Guedes
da Silva, Armando J.L. Pombeiro
PII:
S0022-328X(17)30459-X
10.1016/j.jorganchem.2017.07.030
JOM 20044
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 28 June 2017
Revised Date: 0022-328X 0022-328X
Accepted Date: 24 July 2017
Please cite this article as: A.V. Gurbanov, F.E. Huseynov, A.M. Maharramov, M.Fá.C. Guedes da
Silva, A.J.L. Pombeiro, Cyanosilylation of aldehydes catalyzed by arylhydrazone di- and triorganotin(IV)
complexes, Journal of Organometallic Chemistry (2017), doi: 10.1016/j.jorganchem.2017.07.030.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Di- and triorganotin(IV) complexes with arylhydrazones of active methylene compounds act as
homogeneous catalysts for the cyanosilylation of aldehydes with trimethylsilyl cyanide leading to
cyanohydrin trimethylsilyl ethers in methanol at room temperature

ACCEPTED MANUSCRIPT
Cyanosilylation of aldehydes catalyzed by arylhydrazone
di- and triorganotin(IV) complexes
a,b,c,
c,d
b
Atash V. Gurbanov, * Fatali E. Huseynov, Abel M. Maharramov,
a
a,
M. Fátima C. Guedes da Silva, Armando J. L. Pombeiro *
a
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–
01 Lisbon, Portugal
Department of Chemistry, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan
0
b
c
Organic Chemistry Department, RUDN University, 6 Miklukho-Maklaya str., Moscow 117198, Russian
Federation
d
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:
organik10@hotmail.com (Atash V. Gurbanov)
pombeiro@tecnico.ulisboa.pt (Armando J. L. Pombeiro)
Abstract
1
2
2
Two known organotin(IV) complexes, [Sn(C H ) HL ] (1) and [Sn(C H ) (1κO,2κO-H L )(1κO -
6
5 3
2
5 2
3
2
H L )(µ -O)] (2), were prepared upon interaction of Ph SnCl and Et SnO with 2-(2-(2,4-
3
3
2
3
2
1
dioxopentan-3-ylidene)hydrazinyl)benzoic acid (H L ) and 2-(2-(2,4,6-trioxotetrahydropyrimidin-
2
2
5
(2H)-ylidene) hydrazinyl)benzoic acid (H L ), respectively, in toluene solution. Both complexes
4
are applied as catalysts in cyanosilylation of aldehydes. Complex 2 shows a high catalytic activity
in the cyanosilylation reaction of a variety of aliphatic and aromatic aldehydes with trimethylsilyl
cyanide yielding to the corresponding cyanohydrin trimethylsilyl ethers (yields up to 99 %) in
methanol and at room temperature.
Keywords: Di- and triorganotin(IV) complexes; catalysis; cyanosilylation of aldehydes.
1
. Introduction
The cyanosilylation under study is a Lewis acid/base-catalyzed C−C coupling of an aldehyde and
trimethylsilyl cyanide (TMSCN), to afford cyanohydrin trimethylsilyl ethers (Scheme 1) [1−22].
These compounds are useful intermediates in the synthesis of α-hydroxy acids, α-amino acids, β-
amino alcohols, 1,2-diamines, vicinal diols and other valuable building blocks [1−22]. For the
synthesis of cyanohydrins, TMSCN is a safe and easy to handle source of cyanide compared to
NaCN, HCN and KCN [23]. A variety of organocatalysts such as P(RNCH CH )N [24], N-
2
2
methylmorpholine N-oxide [25], 1,1,3,3-tetramethylguanidine [26], tetraethylammonium 2-(N-
hydroxycarbamoyl)benzoate [27] and N-heterocyclic carbenes [28,29], as well as metal catalysts

ACCEPTED MANUSCRIPT
such as Yb(OTf) [30,31], Yb(CN) [32], Cu(OTf) [33], ZnI [34], KCN:18-crown-6 [35], LiCl
3
3
2
2
and LiClO [36−38], R SnCl an Sn-montmorillonite [39,40], MgBr ·Et O [41], Zr(KPO ) [42],
4
2
2
2
2
4 2
CsF [43,44], VO(OTf) [45], InBr [46], FeCl [47], NbF [48], Fe(Cp) PF [49], Cu(II)-hydrazone
2
3
3
5
2
6
complexes
[50−52],
lead(II)-3-aminopyrazine-2-carboxylate
[53],
lanthanide-containing
polyoxometalates intercalated layered doublehydroxides [54], supported ionic liquid [55] and metal
organic frameworks (MOF's) [56−61], were applied as catalysts for cyanosilation of carbonyl
compounds. Despite extensive development, the ideal catalytic system for a practical and broadly
applicable synthesis of cyanohydrins remains elusive, e.g., most of the listed reports require
prolonged reaction times, harmful solvents, provide rather modest yields, or the reaction must be
performed under heating. Therefore, to develop an efficient cyanosilylation of aldehydes in high
yields with sustainable reaction conditions is a challenge in the field of current organic synthesis.
Scheme 1. Cyanosilylation of aldehydes.
On the other hand, coordination compounds of arylhydrazone ligands have received a great
attention due to their intriguing structural motifs coupled with potential applications [62]. For
instance, Cu(II)-hydrazones show a high catalytic activity in the oxidation of alcohols and alkanes
to the corresponding organic products [62f-n], whereas di- and triorganotin(IV)-hydrazone
complexes exhibit antiproliferative activity [63]. As part of an ongoing project to develop practical,
cheaper and selective catalytic reactions based on hydrazone complexes, we have now found that
the known [63] di- and triorganotin(IV)-arylhydrazone complexes 1 and 2 (Scheme 2) function as
effective catalysts for the addition of trimethylsilyl cyanide (TMSCN) to aliphatic and aromatic
aldehydes.
O
C
O
C
N
N
HN
C
C
C
N
N
C
C
NH
C
C H
C H
2 5
2
5
.
H
.
.
.
.
. . H
.
.
.
.O
C
C
.O
O
N
H
O
O
Sn
O
O
N
H
O
Sn
C
C H
C
2
H
5
2
5
Sn
O
O
Sn
C H
2 5
O
.
. .
O
O
C
2
H
5
Sn
H
3
C
.. H
N
.
C
C
H
H
.
O
. .
O
N
O.
.
.
.
O
O
O...H
N
O
C
C
. H
N
.
C
C H
C
C
C
2
5
C H
2 5
O
N
C
HN
C
N
C
NH
C
O
N
N
C
O
CH
3
1
2
Scheme 2. Schematic representations of complexes 1 and 2 [63].
2

ACCEPTED MANUSCRIPT
2. Experimental
2.1. Materials and instrumentation
1
All the chemicals were obtained from commercial sources (Aldrich) and used as received. H L ,
2
2
1
H L , 1 and 2 were synthesized according to the reported procedure [63]. The H NMR spectra were
4
TM
recorded at room temperature on a Bruker Avance II + 300 (UltraShield Magnet) spectrometer
operating at 300.130 MHz for proton. The chemical shift is reported in ppm using tetramethylsilane
as the internal reference. 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 1100 in methanol
solution. The compounds were observed in the positive mode (capillary voltage = 80–105 V).
2.2. Catalytic activity studies
The solvent (THF, CH Cl or anhydrous MeOH; 2 mL) was added to a flask which contained the
2
2
catalyst (1 or 2) (1–9 mol%) and aldehyde (0.4 mmol), the solution was stirred continuously and the
1
progress of the reaction was followed by TLC. The crude reaction mixture was characterized by H-
1
NMR. The yield of the products was determined by H-NMR [50−52,64−66]. The adequacy of the
1
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 cyanosilylation of benzaldehyde with trimethylsilyl cyanide (TMSCN) was utilized as a model
reaction to explore the effect of the catalysts and various solvents on the yield of cyanohydrin
trimethylsilyl ether, i.e. 2-phenyl-2-((trimethylsilyl)oxy)acetonitrile (Table 1). To evaluate the
catalytic activities of the compounds 1 and 2 and compare them with blank experiments (absence of
1
2
any of these catalysts) and those of the starting materials H L , H L , Ph SnCl and (Et Sn)O, protic
2
4
3
2
(
methanol) and aprotic (1,2-dichloromethane and THF) solvents were applied (Table 1). Catalysts 1
and 2 lead to yields of 2-phenyl-2-((trimethylsilyl)oxy)acetonitrile of 49−84 % in 16 h (entries
−6), which are substantially higher than those obtained in their absence, either in presence or
1
1
2
absence of starting materials H L , H L , Ph SnCl and (Et Sn)O, as well as under solvent-free
2
4
3
2
conditions (entries 7−20). In methanol, the catalytic activity of complex 2 is higher than that of 1
entries 5 and 6), 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. After the screening tests, 2 and methanol were chosen as catalyst and
solvent, respectively, for the further studies.
3

ACCEPTED MANUSCRIPT
a
Table 1. Selection of catalyst for the cyanosilylation of benzaldehyde with TMSCN.
Amount of catalyst
b
Entry
Catalyst
Time (h)
Solvent
Yield (%)
(
mol%)
1
2
3
4
5
6
7
8
9
1
2
1
2
1
2
H2L
H4L
H2L
H4L
16
16
16
16
16
16
16
16
16
16
16
16
16
16
48
6 days
24
16
5
5
5
5
5
5
5
5
5
5
5
5
5
5
-
THF
THF
49.1
53.7
60.8
66.3
74.4
83.9
14.5
15.8
16.7
17.7
26.1
27.9
45.2
38.6
17.1
45.0
14.0
22.3
13.0
20.0
CH Cl2
2
CH Cl2
2
MeOH
MeOH
THF
1
2
THF
1
CH Cl2
2
2
1
1
1
1
1
1
1
1
1
1
2
0
1
2
3
4
5
6
7
8
9
0
CH Cl2
2
1
H2L
H4L
Ph SnCl
(Et Sn)O
MeOH
MeOH
MeOH
MeOH
2
3
2
-
-
-
-
-
-
CH Cl2
2
-
-
-
-
CH Cl2
2
THF
MeOH
16
24
-
-
-
a
Reaction conditions: solvent (2 mL), TMSCN (0.6 mmol) and aldehyde (0.4 mmol), in air at room temperature.
Determined by H NMR analysis of crude products.
b
1
In order to optimize the reaction conditions, we evaluated the effect of the reaction time,
temperature, and influence of different amounts of 2 on the cyanosilylation of benzaldehyde with
TMSCN (Table 2). As shown in Table 2, the reaction was complete after 2 h (Table 2, entry 3) and
3
mol% of 2 was found to be sufficient obtaining the maximum yield (entry 7). The temperature
o
variation (in the 15−55 C range) had only a small effect on the yield (entries 3, 10−13) and hence
room temperature was typically used.
Table 2. Evaluation of reaction conditions of cyanosilylation of benzaldehyde with TMSCN
a
catalyzed by 2.
Amount of catalyst
b
Entry
Time (h)
T (˚C)
Yield (%)
(
mol%)
1
2
3
4
0.5
1
2
5
5
5
5
25
25
25
25
67.1
78.7
83.8
83.9
3
5
6
7
8
9
2
2
2
2
2
1
2
3
4
5
25
25
25
25
25
56.2
74.6
83.7
83.8
83.8
1
1
1
1
0
1
2
3
2
2
2
2
3
3
3
3
15
35
45
55
81.8
84.9
85.0
85.1
a
Reaction conditions: MeOH (2 mL), TMSCN (0.6 mmol) and benzaldehyde (0.4 mmol), in air.
Determined by H NMR analysis of crude products (see Experimental part).
b
1
4

ACCEPTED MANUSCRIPT
In order to verify the scope of the reaction, a series of aliphatic and aromatic aldehydes was
subjected to the cyanosilylation reaction under the optimized reaction conditions, and the results are
presented in Table 3. The overall yields of products are in the range of 80−99% (Table 3). The
length of alkyl chains at the aliphatic aldehydes has a slight effect on the yield of the corresponding
cyanohydrin trimethylsilyl ethers, but they displayed better results (98−99%, entries 1−6) than
aromatic aldehydes (80−88%, entries 6−15, Table 3). In general, aromatic aldehydes with a para
electron-withdrawing group (−Br, −Cl or –NO ) gave higher yields (Table 3, entries 10−12) as
2
compared to those having electron-donating substituents [−CH , −OCH or −N(CH ) ] (entries
3
3
3 2
6−8). To test the electronic and steric effects of the substrate on the cyanosilylation reaction, 2-
methylbenzaldehyde, 2,4,6-trimethylbenzaldehyde and cinnamaldehyde as the substrates (Table 3,
entries 13−15) were employed. With the sterically hindered 2,4,6-trimethylbenzaldehyde, the yield
was the lowest one (Table 3, entry 14).
a
Table 3. Addition of TMSCN to various aldehydes catalysed by catalyst 2 in methanol.
b
Entry
Substrate
Yield (%)
1
2
3
4
5
6
CH CH CHO
3
2
99.3
CH
CH
CH
CH
(CH
(CH
(CH
(CH
)
CHO
CHO
CHO
CHO
99.0
3
3
3
3
2
2
2
2
2
3
4
5
)
)
)
98.4
98.1
97.6
81.8
7
8
9
82.7
82.9
83.7
84.1
84.7
1
1
0
1
1
1
2
3
87.8
83.2
8
0.1
1
1
4
5
84.8
a
Reaction conditions: 3 mol% of catalyst 2, MeOH (2 mL), TMSCN (0.6 mmol) and aldehyde (0.4 mmol). Reaction
b
1
time: 2 h. Determined by H NMR analysis of crude products.
5

ACCEPTED MANUSCRIPT
Up to date the reported cyanosilylation reactions were performed usually in heterogeneous
systems, and there are scant examples of homogeneous ones were reported [1]. Our catalytic system
has several advantages in comparison to the other reported homogeneous systems. For example, a
o
Ti(IV) system required a long reaction time (48 h) and low temperature (-20 C) [67], a Zn(II)
o
system provided low yield (30%) and required a low temperature (0 C) [68], a Cu(II) system also
o
provided a low yield (27%), long reaction time (48 h) and high temperature (40 C) [69], and an
o
Al(III) one required a long reaction time (18 or 96 h) and a low temperature of -50 or -40 C
[
70,71].
As reported for related catalytic systems [6,51], the metal centre and the NH of pyrimidine
moiety can act cooperatively, polarising the carbonyl group of the aldehyde and facilitating the
attack of TMSCN to form the cyanohydrin trimethylsilyl ethers. The pyrimidine free C=O moiety
(as an electron acceptor center) of the catalyst may also enhance the nucleophilic attack of cyanide
on aldehyde.
4. Conclusions
Two previously reported di- and triorganotin(IV) complexes bearing arylhydrazones of active
methylene compounds [63] have been prepared and applied as catalysts in the cyanosilylation of
aliphatic and aromatic aldehydes with trimethylsilyl cyanide. Possibly on account of 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 cyanohydrin trimethylsilyl
ethers in high yields (80−99%) in 2 h. When aliphatic aldehydes were used as the starting materials
the yield of cyanohydrin trimethylsilyl ethers is higher (98−99%) than for the aromatic ones
(80−88%). The Electron-withdrawing or -donor character of a substituent in the para position of the
aromatic aldehydes has promoting or inhibiting effect, respectively, on the reaction yield.
Moreover, in comparison to previously reported homogeneous catalysts, our diorganotin-
arylhydrazone catalysts exhibit higher catalytic activity and this system operates smoothly 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).
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.
6

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Highlights
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Di- and triorganotin(IV) complexes with arylhydrazones of active methylene compounds
Catalytic activity of diorganotin(IV) complex is high in homogeneous cyanosilylation of aldehydes
in methanol at room temperature
This system uses low catalyst amount, does not require long reaction time
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