Specific 1,2-Hydride Shift in the Boron Trifluoride Catalyzed Reactions of Aromatic Aldehydes with Diazoacetonitrile: Simple Synthesis of β-Ketonitriles

Article abstract of DOI:10.1002/ejoc.201402901

A series of β-ketonitriles was synthesized within 30 min under mild conditions through the BF₃ ·OEt₂-catalyzed addition reactions of diazoacetonitrile to aromatic aldehydes and subsequent 1,2-hydride shift. This method is advantageous in that it is operationally simple, mild and metal-free conditions are used, the substrate scope is wide, and the products are obtained in moderate to high yields (up to 81 %). Additionally, γ,δ-unsaturated β-ketonitriles are also accessible by this method by using cinnamaldehydes.

Full text of DOI:10.1002/ejoc.201402901

SHORT COMMUNICATION
DOI: 10.1002/ejoc.201402901
Specific 1,2-Hydride Shift in the Boron Trifluoride Catalyzed Reactions of
Aromatic Aldehydes with Diazoacetonitrile: Simple Synthesis of β-Ketonitriles
[a]
[a]
[a]
[a]
[a]
Zhanhui Yang, Kwon-Il Son, Siqi Li, Bingnan Zhou, and Jiaxi Xu*
Keywords: Synthetic methods / Nucleophilic addition / Hydride shift / Ketonitriles / Aldehydes / Diazo compounds
A series of β-ketonitriles was synthesized within 30 min un-
der mild conditions through the BF ·OEt -catalyzed addition
reactions of diazoacetonitrile to aromatic aldehydes and sub-
sequent 1,2-hydride shift. This method is advantageous in
that it is operationally simple, mild and metal-free conditions
are used, the substrate scope is wide, and the products are
obtained in moderate to high yields (up to 81%). Addition-
ally, γ,δ-unsaturated β-ketonitriles are also accessible by this
method by using cinnamaldehydes.
3
2
Introduction
β-Ketonitriles are an important class of intermediates in
organic synthetic chemistry. On the basis of the activities of
the ketyl, cyano, and active methylene groups, numerous
reports have been documented on the use of β-ketonitriles
[
1]
to synthesize a variety of very important structures. In
contrast to the wide applications of β-ketonitriles, only a
limited number of synthetic methods exist. In general, the
published methods can be categorized into the following
four types (Scheme 1): condensation of esters or Weinreb
amides of aromatic carboxylic acids with acetonitriles in the
presence of strong bases (path a),[ substitution of irritant
and unstable α-haloketones with extremely toxic cyanide
anions (path b),[ expensive Pd-catalyzed carbonylation of
2]
3]
aryl iodides and (trimethylsilyl)acetonitriles with high-pres- Scheme 1. Reported methods for the synthesis of β-ketonitriles;
[
4]
DEPC = diethyl phosphorocyanidate.
sure CO (path c), and the CuCl -catalyzed aerobic oxidat-
2
ive coupling of arylmethanols with acetonitrile by using the
high-boiling-point solvent N,N-dimethylacetamide (DMA)
The Büchner–Curtius–Schlotterbeck reaction generally
and an excess amount of strong base (path d).[ Other un- refers to the reaction of aldehydes or ketones with aliphatic
5]
[
8]
satisfactory methods include the solid-phase C-acylation of diazoalkanes to generate homologated ketones. If alde-
the active methylene group of cyanoacetates by using a hydes are employed as the substrates, three possible prod-
large excess amount of the coupling reagents followed by ucts can be generated (Scheme 2) through (1) 1,2-hydride
[
6]
decarboxylation with trifluoroacetic acid (TFA, path e),
and the indium-mediated coupling of the irritant bromo- shift to yield α,α-disubstituted aldehydes, and (3) intra-
shift to afford α-functionalized ketones, (2) 1,2-alkyl/aryl
[
7]
acetonitrile with toxic aromatic acyl cyanides (path f).
molecular nucleophilic substitution to produce epoxides.
Therefore, the development of a simple and convenient The competition of these three pathways is dependent on
method to synthesize β-ketonitriles under mild, metal-free, the electronic and steric features of substrates and on the
[
9–14]
and safe conditions is still in demand.
conditions employed.
Generally, reactions of monosub-
stituted active diazoalkanes (RCHN ) with aldehydes or
2
cyclic ketones generate complex products without good
[
a] State Key Laboratory of Chemical Resource Engineering;
Department of Organic Chemistry, Faculty of Science, Beijing chemoselectivity.
University of Chemical Technology,
[
10]
However, reactions of stable diazo-
alkanes with electron-withdrawing functionalities (EWG-
No. 15 Northern 3rd Ring Road East, Chaoyang District,
Beijing 100029, People’s Republic of China
3
2
3
CN
R ) or those with two substituents (R R CN ) can oc-
2
2
E-mail: jxxu@mail.buct.edu.cn
cur with high chemoselectivity, which can be controlled by
http://sci.buct.edu.cn/szll/jsml/yjhxx/9746.htm
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201402901.
[
11,12]
Brønsted/Lewis acid catalysts
of the diazoalkanes.
or by substituent effects
[
10,14]
Roskamp and co-workers re-
6380
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2014, 6380–6384

Simple Synthesis of β-Ketonitriles
ported the SnCl -catalyzed reactions of aldehydes with 12 h, no product was observed by TLC monitoring (Table 1,
2
[
11a]
[11b]
diazoacetate,
ides,
diazosulfones,
diazophosphine ox- entry 1). We supposed that the stability of diazoacetonitrile
to synthesize the corre- prevented the reaction. Thus, we decided to add different
[
11b]
[11b]
and diazophosphonates
sponding synthetically useful structures. Aliphatic alde- acids into the system to activate 1a and to initiate the reac-
hydes were predominantly used to guarantee that 1,2- tion. Initial screening with Brønsted acids such as acetic
hydride shift predominated over 1,2-alkyl shift. However, if acid, TFA, and p-toluenesulfonic acid (TsOH) gave disap-
aromatic aldehydes are used as substrates, the desired prod- pointing results, and no desired products were detected by
ucts are obtained in low yields, presumably as a result of TLC (Table 1, entries 2–4). This led us to further consider
the predominance of 1,2-aryl shift over 1,2-hydride shift. Lewis acids as catalysts. Metal salt Lewis acids such as
Subsequent studies from other groups successfully reported AlCl , SnCl ·2H O, FeCl , FeSO ·7H O, ZnCl , CuCl ,
3
2
2
3
4
2
2
2
the predominance of 1,2-hydride shift over 1,2-aryl shift by and CuCl were examined. Except for SnCl ·2H O,
2
2
using different catalysts.[ However, if other diazoalkanes all the other catalysts failed (Table 1, entries 5–11). Al-
12]
are used to react with aromatic aldehydes, the results are though SnCl ·2H O was very efficient in catalyzing the re-
2
2
[
11a,11c]
still obscure, as exemplified by Carreira and co-workers in actions of aldehydes with diazoesters,
diazosulf-
and diazophosphon-
it did not work efficiently under our reaction con-
[
11b]
[11b]
the synthesis of α-trifluoromethyl ketones through the ones,
diazophosphine oxides,
[
11b]
ZrCl -catalyzed reactions of aromatic aldehydes with tri- ates,
4
[13]
fluoromethyl diazomethane.
Thus, the spontaneous pre- ditions, and 3a was obtained in an unsatisfactory yield of
dominance of 1,2-aryl shift over 1,2-hydride shift[ poses 30% after 12 h (Table 1, entry 6). Finally, we tested
14]
a big challenge in synthesizing α-functionalized aryl ketones BF ·OEt as the catalyst. To our surprise, aldehyde 1a was
3
2
through the Büchner–Curtius–Schlotterbeck reaction of completely consumed within 5 min, and desired product 3a
aromatic aldehydes and stable diazoalkanes, and the control was isolated in a good yield of 70% (Table 1, entry 12).
of the chemoselectivity on 1,2-aryl, -alkyl, and -hydride Despite its significant catalytic efficiency in reactions in-
[
16a,16c,16d]
shifts is still one of the most topical issues in this field.
volving diazo compounds as carbene precursors,
Rh (OAc) could not catalyze the current reaction (Table 1,
2
4
entry 13), which to some extent implies that a carbene inter-
mediate is not involved.
Table 1. Optimization of the reaction conditions.[a]
Entry
Catalyst
Time [min]
Yield [%]
Scheme 2. Diverse pathways of the Büchner–Curtius–Schlotterbeck
reaction.
1
2
3
4
5
6
none
AcOH
TFA
720
60
60
60
60
720
5
60
60
5
60
5
720
5
0
0
0
0
In continuation of our interest in diazo compounds,[15,16]
TsOH·H
2
O
for the first time, we explored the reactions between alde-
hydes and diazoacetonitrile, which can be easily prepared
from commercially available aminoacetonitrile hydrochlor-
ide and sodium nitrite.[ As an active cyanomethyl donor,
diazoacetonitrile has not received much attention in the
AlCl
SnCl
FeCl3
FeSO
3
0[c]
2
·2H
2
O
30
[
b]
7
8
9
1
1
1
0
0
0
0
0
17]
4
·7H
2
O
ZnCl
CuCl
CuCl
2
0[
1
2
d]
[
18]
2
synthetic community,
despite the fact that the introduc-
[e]
tion of a cyano group is a hot research topic.[ In this
19]
[d]
[f]
BF
Rh
BF
3
·OEt
2
(OAc)
3
·OEt
2
70
[
[
g]
h]
work, the chemoselectivity in the BF ·OEt -catalyzed reac- 13
4
0
3
2
[f]
14
2
17
tions of aromatic aldehydes with diazoacetonitrile was suc-
cessfully controlled. The reactions proceed predominantly [a] Reactions were conducted with benzaldehyde (1a; 53 mg,
0
.5 mmol) and diazoacetonitrile (2; ca. 50 mg, 0.75 mmol, 4 mL
through 1,2-hydride shift rather than through 1,2-aryl shift;
consequently, a simple method to synthesize β-ketonitriles
is presented.
solution). [b] Upon the addition of FeCl , 2 was completely con-
3
sumed within 5 min; however, only a trace amount of α-cyano-
acetophenone (3a) and large amount of 1a were observed by TLC.
[c] Yield of isolated product after stirring the mixture at room tem-
perature for 12 h; 3a was detected after 1 h, but 1a was not com-
pletely consumed. [d] Diazoacetonitrile (2) was completely con-
sumed within 3 min upon its addition. [e] After about 1 h, diazo-
acetonitrile (2) was completely consumed, but no product was de-
tected by TLC. [f] Yield of isolated product after stirring for an-
Results and Discussion
Initially, we started our optimization of the reaction con-
ditions by simply mixing benzaldehyde (1a) with diazo-
other 2 min upon the addition of 2. [g] Rh
2
(OAc)
4
(1 mol-%) was
acetonitrile (2) in CH Cl . However, after stirring for about used. [h] Reaction was conducted at –78 °C.
2
2
Eur. J. Org. Chem. 2014, 6380–6384
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org 6381

Z. Yang, K.-I. Son, S. Li, B. Zhou, J. Xu
SHORT COMMUNICATION
There was one confusing fact: aldehyde 1a was com- applications because of their additional active alkene moi-
pletely consumed, but desired product 3a was isolated in ety.
only 70% yield. We wanted to determine what the remain-
ing 30% of the aldehyde was converted into. TLC analysis Table 2. Reaction of aldehydes 1 and diazoacetonitrile (2).[a]
showed that another product with greater polarity might be
present, but analysis of the isolated product (ca. 10 mg) by
1
H NMR spectroscopy indicated a very complex mixture,
and no epoxide product resulting from intramolecular nu-
cleophilic substitution or aldehyde product resulting from
1
–
,2-phenyl shift was detected. Conducting the reaction at
78 °C gave no 1,2-phenyl shift product. The desired prod-
uct 3a was isolated in 17% yield, with benzaldehyde reco-
vered in 79% (Table 1, entry 14). Thus, we believe the cur-
rent reaction proceeds through a specific 1,2-hydride shift
pathway, and this conclusion was verified by the reactions
in the substrate scope extension step.
With the optimal conditions, we explored the substrate
scope of this method by using diversely substituted aro-
matic aldehydes. The results are presented in Table 2. To
our delight, modification of the para position of the phenyl
ring with various electron-donating groups, such as 4-
methyl (1b), 4-isopropyl (1e), and 4-methoxy (1f) groups did
not have a significant influence on the reactions, and de-
sired products 3b, 3e, and 3f were delivered in 75, 50, and
79% yield, respectively (Table 2, entries 2, 5, and 6). Sub-
stituents on the phenyl ring imposed little impact on the
yields of the reaction (Table 2, entries 2–4 and 7). Next, we
assessed the influence of weak electron-withdrawing groups
on the phenyl ring. 4-Fluorobenzaldehyde (1h) and 2-
fluorobenzaldehyde (1i) had a slight impact, and corre-
sponding products 3h and 3i were isolated in satisfactory
yields of 77 and 87%, respectively (Table 2, entries 8 and
9). Surprisingly, compared with 3-chlorobenzaldehyde (1k,
Table 2, entry 11), 4-chlorobenzaldehyde (1j) and 2-chloro-
benzaldehyde (1l) showed some influence on the reaction,
and corresponding products 3j and 3l were isolated in 48
and 60% yield, respectively (Table 2, entries 10 and 12). 4-
Bromobenzaldehyde (3m) and 4-phenylbenzaldehyde (3n)
were readily converted into the corresponding products in
yields of 72 and 56%, respectively (Table 2, entries 13 and
14). Subsequent experiments with benzaldehydes substi-
tuted with strong electron-withdrawing groups such as
cyano (1o) and nitro (1p) groups gave good results, and
products 3o and 3p were isolated in 75 and 82%
yields, respectively (Table 2, entries 15 and 16). Addition-
ally, other aromatic aldehydes such as 2-thiophenaldehyde
[
a] All the reactions were conducted on a 0.5 mmol scale. [b] Pro-
cedure A: BF ·OEt (20 mol-%) was used within 5 min. Pro-
cedure B: BF ·OEt (20 mol-% + 20 mol-% + 20 mol-%) was used
within 30 min. For details, see the Experimental Section. [c] Yields
3
2
3
2
(1q), 2-furaldehyde (1r), 1-naphthaldehyde (1s), and 2-
naphthaldehyde (1t) were suitable substrates, and corre- of isolated products.
sponding products 3q, 3r, 3s, and 3t were produced in mod-
erate yields of 69, 65, 64, and 72%, respectively (Table 2,
Application of this method to a large-scale synthesis was
entries 17–19). Aliphatic aldehyde 1u was also evaluated in also tested (Scheme 3). On a 10 mmol scale, the synthesis
this reaction, but unfortunately no product was obtained of 3-oxo-3-phenylpropanenitrile (3a) proceeded smoothly,
(Table 2, entry 20), which reveals that the current condi- and it was obtained in 65% yield (0.95 g).
tions are not applicable to aliphatic aldehydes. However, A plausible mechanism for the formation of β-keto-
[
20]
cinnamaldehyde (1v) was susceptible to this transformation, nitriles is proposed in Scheme 4. Under the activation of
and γ,δ-unsaturated β-ketonitrile 3v was obtained in 49% BF ·OEt , aromatic aldehyde 1 is attacked by diazoaceto-
3
2
yield (Table 2, entry 21). Compared with β-ketonitriles, nitrile (2) to form intermediate A, which evolves nitrogen
γ,δ-unsaturated β-ketonitriles have much more potential gas and undergoes 1,2-hydride shift to give rise to product
6382
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Eur. J. Org. Chem. 2014, 6380–6384

Simple Synthesis of β-Ketonitriles
Preparation of Diazoacetonitrile (2): Following a simplified version
17]
of
4.63 g, 50 mmol) was dissolved in water (10 mL) in a 50 mL
round-bottomed flask immersed in an ice-water bath, and then
CH Cl (20 mL) was added. The mixture was stirred vigorously,
and sodium nitrite (3.45 g, 50 mmol) was added over 5 min. After
stirring for another 15 min, the mixture was extracted with CH Cl
50 mL). Washing with saturated aqueous NaHCO solution and
drying with Na SO gave a solution of diazoacetonitrile (65 mL),
. Although the 1,2-aryl shift pathway was observed as the which was stored in a refrigerator (ca. –4 °C). The yield was esti-
sole pathway in the reaction of piperanol with diazometh- mated to be 30% by measuring the mass of the product in an ali-
a
literature procedure,[
aminoacetonitrile hydrochloride
(
2
2
Scheme 3. Large-scale synthesis of β-ketonitriles.
2
2
(
3
2
4
3
[
10a–10c]
quot portion of the dichloromethane solution (41 mg/2.5 mL) after
removing the solvent at 0 °C under vacuum. The yield was im-
proved to 60–70% if more complex operations were performed ac-
cording to Dewar’s procedure.[
ane
and in the reaction of 3-methoxybenzaldehyde
[13]
with (trifluoromethyl)diazomethane,
it was not the pre-
dominant pathway in our reaction system, which is indica-
tive of the high chemoselectivity of the present reaction.
The 1,2-hydride shift is more predominant than the 1,2-aryl
17]
Typical Procedures for the Synthesis of β-Ketonitriles 3
3 2
shift, possibly as a result of the hyperconjugation of the Procedure A: BF ·OEt (0.1 mmol, 13 μL) was added to a solution
of aldehyde 1 (0.5 mmol) in dichloromethane (1 mL) in a 25 mL
tube. A solution of diazoacetonitrile (0.75 mmol, ca. 4 mL) was
then added over 1 min, and a large amount of nitrogen gas evolved.
When the evolution of nitrogen gas ceased (within 5 min), the mix-
ture was concentrated and subjected to column chromatography
C–H bond and the generated carbocation after release of
nitrogen gas. We believe that the cyano group plays an im-
portant role in facilitating the 1,2-hydride shift, possibly by
assisting hyperconjugation through its strong electron-with-
drawing ability. However, details are still not clear, and fur-
ther systematic computational studies are in progress.
[silica gel, petroleum ether (60–90 °C)/EtOAc] to give product 3.
Procedure B: BF ·OEt (0.1 mmol, 13 μL) was added to a solution
3
2
of aldehyde 1 (0.5 mmol) in dichloromethane (1 mL) in a 25 mL
tube. A solution of diazoacetonitrile (0.75 mmol, ca. 4 mL) was
then added over 1 min; a large amount of nitrogen gas evolved.
The reaction mixture was monitored by TLC, and after 5 min alde-
hyde 1 was not completely consumed. Another portion of
BF
3
·OEt
2
(0.1 mmol, 13 μL) was added, and a large amount of
·OEt
0.1 mmol, 13 μL) was added, and the mixture was stirred for
nitrogen gas evolved. After 5 min, an extra amount of BF
(
3
2
20 min to ensure complete consumption of the aldehyde, as de-
tected by TLC. The mixture was concentrated and subjected to
column chromatography [silica gel, petroleum ether (60–90 °C)/
EtOAc] to give product 3.
Scheme 4. Proposed mechanism for the formation of β-ketonitriles.
Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedure for the large-scale preparation of β-
1
ketonitriles 3, analytical data and copies of the H NMR and
C NMR spectra of products β-ketonitriles 3.
Conclusions
1
3
In conclusion, we developed a mild synthesis of β-keto-
nitriles by successfully controlling a specific 1,2-hydride
shift in the BF ·OEt -catalyzed reactions of aromatic alde-
Acknowledgments
3
2
hydes with diazoacetonitrile; the reaction is advantageous The project was supported by the National Basic Research Pro-
in that it is operationally simple, mild and metal-free condi- gram of China (grant number 2013CB328905) and the National
Natural Science Foundation of China (NSFC) (grant numbers
tions are used, and the products are obtained in moderate
21172017 and 21372025).
to high yields (up to 87%). The starting aromatic aldehydes
are commercially available and cheap, diazoacetonitrile is
easily prepared, and the catalyst (BF ·OEt ) is easily access-
[
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6383

Z. Yang, K.-I. Son, S. Li, B. Zhou, J. Xu
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Received: July 10, 2014
Published Online: September 8, 2014
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