TBD-catalyzed cyanosilylation of aldehydes and ketones

Article abstract of DOI:10.1080/00397911.2016.1241884

This study examines the catalytic efficacy of 1,5,7-triazabicyclo[4,4,0]dec-5-ene (TBD) in the cyanosilylation of aldehydes and ketones. In an aldehyde reaction, the corresponding products were obtained at high yield using minimal TBD (0.01 mol%). TBD was

Full text of DOI:10.1080/00397911.2016.1241884

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TBD-catalyzed cyanosilylation of aldehydes and
ketones
S. Matsukawa & J. Kimura
To cite this article: S. Matsukawa & J. Kimura (2016) TBD-catalyzed cyanosilylation
of aldehydes and ketones, Synthetic Communications, 46:23, 1947-1952, DOI:
10.1080/00397911.2016.1241884
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Date: 17 November 2016, At: 02:42

SYNTHETIC COMMUNICATIONS®
016, VOL. 46, NO. 23, 1947–1952
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http://dx.doi.org/10.1080/00397911.2016.1241884
TBD-catalyzed cyanosilylation of aldehydes and ketones
S. Matsukawa and J. Kimura
Department of Science Education, Faculty of Education, Ibaraki University, Mito, Ibaraki, Japan
ABSTRACT
ARTICLE HISTORY
Received 15 August 2016
This study examines the catalytic efficacy of 1,5,7-triazabicyclo[4,4,0]dec-
5
-ene (TBD) in the cyanosilylation of aldehydes and ketones. In an
KEYWORDS
Base catalyst;
cyanosilylation; guanidine;
organocatalyst
aldehyde reaction, the corresponding products were obtained at high
yield using minimal TBD (0.01 mol%). TBD was similarly effective in
various ketone reactions.
GRAPHICAL ABSTRACT
Introduction
The addition of trimethylsilyl cyanide (TMSCN) to carbonyl compounds (cyanosilylation)
is among the most fundamental carbon–carbon bond-formation reactions in modern
organic chemistry.[1] The resultant cyanohydrins are easily converted into important mole-
cules including α-hydroxyl carbonyl compounds and β-amino alcohols. The efficiency of
this transformation is enhanced by catalytic systems such as Lewis acids, organocatalysts,
[
2]
[3]
metal salts, and inorganic solid acids and bases. Base catalysts, such as phosphines,
phosphonium salts,[4] amines,
[5]
ammonium salts,
[6]
N-oxides,
[7]
guanidine,
[8]
and
[
9]
N-heterocyclic carbine, have also been studied and achieved high efficiency. In this study,
we explore a new catalyst, 1,5,7-triazabicyclo[4,4,0]dec-5-ene (TBD), for the cyanosilylation
reaction.
It is well known that TBD is a strong Lewis base owing to its distorted ring structures.
Consequently, TBD is employed as an organobase catalyst in multiple unique reactions such
[
11]
[
[13]
[17]
as the Henry reaction,
the Michael reaction,
intramolecular aldol reaction,
ring-
14]
[12]
[18]
opening polymerization,
conjugate addition to activated alkenes,
the Wittig and Horner–Wadsworth–Emmons reaction,
[
15]
[16]
ester aminolysis,
pyrazoline synthesis,
[
19]
and others.
Although TBD usually behaves as a base, it also contains an acidic N–H
CONTACT S. Matsukawa
satoru.matsukawa.1@vc.ibaraki.ac.jp
Education, Ibaraki University, Mito, Ibaraki 310-8512, Japan.1
Department of Science Education, Faculty of
13
Supplemental data (experimental details and copies of H and C NMR spectra of products 2a–2j and 4a–4j)
can be accessed on the publisher’s website.
©
2016 Taylor & Francis

1
948
S. MATSUKAWA AND J. KIMURA
[
20]
group; therefore, TBD may act as a bifunctional acid–base catalyst.
Recently, we also
and organocatalyst in
Herein, we report the efficient catalytic activity of TBD
[
21]
employed TBD as the catalyst in aldehyde trifluoromethylation
[
22]
the ring opening of aziridines.
in the cyanosilylation of aldehydes and ketones.
Results and discussion
First, p-anisaldehyde was reacted with trimethylsilyl cyanide in the presence of 1 mol%
TBD in CH CN at room temperature. The reaction proceeded smoothly and the product
3
was obtained in high yield. Next, we reduced the catalyst quantity to 0.1 mol% and
achieved the same smooth reaction. Finally, we found that a product was obtained
in 91% even at 0.01 mol% of TBD. The product was obtained in lower yield when 1,
8
7
-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,1,3,3-tetramethylguanidine (TMG), and
-methyl-TBD (MTBD) were used instead of TBD (Table 1, entries 1 vs. 4–6). These
reactive differences suggest that TBD has a role of both bicyclic strong Lewis base and
acid–base bifunctional catalyst in the cyanosilylation catalysis. We performed a reference
a
Table 1. Cyanosilylation of various aldehydes.
Entry
Cat. (mol%)
Aldehyde
4-CH OC CHO
Time
1 h
Product
Yield (%)
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
1
0.1
0.01
3
6
H
4
2a
98
92
93
b
12 h
12 h
12 h
1 h
32
c
40
d
36
e
85
f
12 h
12 h
0.5 h
0.5 h
2 h
55
g
45
1
1
1
1
1
1
1
1
1
C
6
H
5
CHO
4-ClC CHO
4-NO CHO
2b
2c
2d
2e
2f
83
95
65
91
90
85
79
81
92
6 4
H
2 6 4
C H
α-Naphthaldehyde
β-Naphthaldehyde
2 h
1 h
C
C
6
H
H
8
5
CH
17CHO
11CHO
2-Furaldehyde
2
CH
2
CHO
4 h
2g
2h
2i
2 h
c-C
6
H
2 h
0.5 h
2j
a
b
c
Isolated yield.
MTBD was used instead of TBD.
TMG was used instead of TBD.
d
DBU was used instead of TBD.
In DMF.
e
f
In THF.
g
2 2
In CH Cl .

SYNTHETIC COMMUNICATIONS®
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study of the solvent. Among several candidate solvents (CH CN, tetrahydrofuran [THF],
3
dimethylformamide [DMF], and CH Cl ), CH CN proved to be the most suitable for this
2
2
3
reaction. To clarify the scope of the reaction, we subjected several aldehydes to 0.01 mol%
TBD in CH CN (Table 2). Both aromatic and aliphatic aldehydes reacted smoothly and
3
delivered the products in good to high yields. In the case of 4-nitrobenzaldehyde, the
starting material was rapidly consumed; however, the product yield was not good. In this
case, it is likely that attack at the NO group occurred.
2
Moreover, we investigated the scope of TBD-catalyzed ketone reactions (Table 2). The
ketone reactions required slightly larger catalyst quantities (0.1–0.2 mol%) than the
aldehyde reactions. In this condition, aromatic, aliphatic, acyclic, and cyclic ketones all
delivered good results. Slightly longer reaction times were needed in the reaction of
aromatic aldehydes bearing electron-donating groups on the aromatic ring. Only
1
,2-addition products were observed for benzalacetone and chalcone.
A possible mechanism is illustrated in Scheme 1. First, TBD coordinates the silicon atom
of the TMSCN and the C-Si bond is activated (A). Next, hydrogen bond activates the
carbonyl compound with the same molecule of TBD occurs (B). Both activated molecules
can then readily react to produce the alkoxide anion of the cyanohydrin (C) and silylated
a
Table 2. TBD-catalyzed cyanosilylation of various ketones.
Entry
1
Ketones
Cat. (mol%)
0.1
Time
2 h
Product
Yield (%)
77
4a
2
3
4
5
6
4 h
2 h
2 h
1 h
4 h
4b
4c
4d
4e
4f
88
94
87
89
85
0.2
0.1
7
8
9
0.2
0.2
0.1
0.5
4 h
1 h
4 h
1 h
4g
4h
4i
92
83
82
94
10
4j
a
Isolated yield.

1
950
S. MATSUKAWA AND J. KIMURA
Scheme 1. Proposed mechanism.
TBD (D). Finally, silylation between the the alkoxide anion and silylated TBD occurs to
give the silylated adduct with regeneration of TBD.
Conclusion
In conclusion, we demonstrated that TBD catalyzes the cyanosilylation of aldehydes and
ketones. The corresponding products of a broad range of aldehydes were obtained at high
yield under mild conditions using minimal TBD (0.01 mol%). TBD was similarly effective
in the cyanosilylation of various ketones.
Experimental
Representative experimental procedures for TBD-catalyzed cyanosilylation of
carbonyl compounds with TMSCN
A 1-mM solution of TBD/CH CN (10 μL, 0.01 µmol to 100 μL, 0.1 µmol) was added to a
3
solution of carbonyl compounds (1.0 mmol) and TMSCN (1.1 mmol) in CH CN (1 mL) at
3
room temperature. After the reaction was complete (as determined by thin-layer chroma-
tography, TLC), the reaction mixture was quenched with water. The resultant mixture was
extracted with EtOAc (3 � 10 mL). The combined organic layers were washed with water
and brine and dried with Na SO . After the filtration, the residue was concentrated
2
4
in vacuo. The crude product was purified by column chromatography on silica gel
EtOAc/hexane ¼ 1:10) to give the corresponding product as silylated form.
(
2
-Phenyl-2-trimethylsilyloxyacetonitrile (2a)[5a]
The title compound was prepared according to the general procedure and the product was
1
obtained as a colorless oil. Yield: 98% (0.231 g); H NMR (500 Hz, CDCl ) δ 0.22 (s, 9H),
3

SYNTHETIC COMMUNICATIONS®
1951
.49 (s, 1H), 7.36–7.43 (m, 3H), 7.46 (d, J ¼ 7.5 Hz, 2H); 3C NMR (125 MHz, CDCl3)
1
5
δ-0.3, 63.7, 119.1, 126.3, 128.9, 129.3, 136.3.
2
-Phenyl-2-trimethylsilyloxypropanenitrile (4a)[5a]
The title compound was prepared according to the general procedure and the product was
1
obtained as a colorless oil. Yield: 77% (0.169 g); H NMR (500 Hz, CDCl ) δ 0.15 (s, 9H),
3
13
1
1
.84 (s, 3H), 7.30–7.40 (m, 3H), 7.52 (d, J ¼ 8.2 Hz, 2H); C NMR (125 MHz, CDCl ) δ
3
.0, 35.6, 71.6, 121.7, 124.6, 128.6, 142.0.
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