Indium(I) bromide-mediated coupling of dibromoacetonitrile with aldehydes followed by Boord elimination of bromine and oxygen of β-bromo alkoxides for preparation of 3-organyl-2-alkenenitriles

Article abstract of DOI:10.1016/j.jorganchem.2006.01.039

The organoindium compound derived from indium monobromide and dibromoacetonitrile reacts with carbonyl compounds to afford the corresponding 2-bromo-2-cyano-indium(III) alkoxide. The action of a second equivalent of indium monobromide onto the alkoxides derived from aldehydes promotes the Boord elimination of the β-related oxygen and bromine atoms leading to 2-alkenenitriles.

Full text of DOI:10.1016/j.jorganchem.2006.01.039

Journal of Organometallic Chemistry 691 (2006) 2335–2339
www.elsevier.com/locate/jorganchem
Communication
Indium(I) bromide-mediated coupling of dibromoacetonitrile
with aldehydes followed by Boord elimination of bromine and oxygen
of b-bromo alkoxides for preparation of 3-organyl-2-alkenenitriles
*
Clovis Peppe , Paola de Azevedo Mello, Rafael Pavao das Chagas
˜
ˆ
´
Laborato´rio de Materiais Inorganicos, Departamento de Quımica, Universidade Federal de Santa Maria, Santa Maria-RS 97105-900, Brazil
Received 19 December 2005; received in revised form 20 January 2006; accepted 20 January 2006
Available online 28 February 2006
Abstract
The organoindium compound derived from indium monobromide and dibromoacetonitrile reacts with carbonyl compounds to afford
the corresponding 2-bromo-2-cyano-indium(III) alkoxide. The action of a second equivalent of indium monobromide onto the alkoxides
derived from aldehydes promotes the Boord elimination of the b-related oxygen and bromine atoms leading to 2-alkenenitriles.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Indium; Organoindium; Carbon–carbon bond formation; Boord elimination; Oxygen extrusion; Sequenced chemical reactions
1. Introduction
R2 [1]. Organoindium species with electrophilic organyl
substituents results from an interaction of the lone pairs
of electrons on the a-halide substituent with an empty
metal orbital (R1 = R2 = H; X = Br, I). a,a-Dihalogeno-
nitriles [2] and a,a-dihalogenoketones [3] produce organo-
metallics containing nucleophilic organyl substituents,
and as such they conveniently couple with carbonyl com-
pounds leading to new carbon–carbon bonds. In this work,
we focus on the reaction involving InBr, dibromoacetonit-
rile and carbonyl compounds, which produced a novel
example of sequenced chemical reactions promoted by
InBr.
Sequenced chemical reactions are an attractive new tool
for the synthetic organic chemist. They provide a single-
step process, normally carried out in one-pot, to a desired
target molecule, whose formation needs several chemical
transformations. The stored information acquired while
studying the chemical properties of indium(I) compounds
made possible the development of a new example of
sequenced chemical reactions, mediated by indium(I) salts,
leading to useful organic substances.
The most characteristic reaction of indium(I) com-
pounds is the oxidative insertion into a suitable chemical
bond [1]. Indium monohalides, for instance, are easily
oxidized to the corresponding dihalogeno-a-halogeno-
alkyl-indium(III) compounds by insertion into one of the
carbon–halogen bonds of gem-dihalogenoalkane deriva-
tives (Scheme 1).
2. Results and discussion
Scheme 2 shows the sequenced reactions. We have dem-
onstrated that the primary organometallic intermediate,
(bromo-cyano-methyl)-dibromo-indium(III), 1 couples effi-
ciently with selected carbonyl compounds, 2 to afford the
indium(III) alkoxide, 3 [2]. The action of one molar equiv-
alent of InBr on the alkoxide 3, in refluxing THF, produces
the organodimetallic intermediate, 4 believed to be the key
intermediate leading to the alkenenitrile, 5. The transfor-
mation 3 ! 5, which is verified only in reactions involving
The electronic character of the a-halogenoalkylic carbon
atom is determined by the nature of its substituents, R1 and
*
Corresponding author. Tel.: +55 55 3220 8868; fax: +55 55 3220 8031.
E-mail address: peppe@quimica.ufsm.br (C. Peppe).
0022-328X/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.01.039

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C. Peppe et al. / Journal of Organometallic Chemistry 691 (2006) 2335–2339
Table 1
R1
X
R1
R2
X
X
Indium(I) bromide-promoted preparation of alkenenitriles
R2
Br
+
InX
In
R
CN
R
2 InBr
O
+
X
NC
X
THF, Δ,
14 h
2
5
Scheme 1. Oxidative insertion of InX into the carbon–halogen bond of
Br
52-88 %
gem-dihaloalkanes.
Entry
R
Yield (%)
Z/E
a
b
c
C6H5
88
65
80
73
71
53
63
62
62
52
60
63
55
1.4/1.0
1.4/1.0
1.0/1.2
1.0/3.5
2.2/1.0
1.0/1.2
1.0/2.6
1.2/1.0
1.0/1.5
1.2/1.0
1.3/1.0
1.3/1.0
1.8/1.0
o-Cl–C6H4
p-Cl–C6H4
p-Cl–C6H4
o-Br–C6H4
p-Br–C6H4
p-Br–C6H4
p-CH3–C6H4
o-CH3O–C6H4
p-CH3O–C6H4
nC6H13
nC9H19
(E)–C6H5–CH@CH
Br
InBr
2 InBr +
R1R2CO
a
NC
d
e
Δ
Br
a
Br
Br
f
R1
R2
CN
g
h
i
j
k
a
In
CN
Br
5
1
R1
R2
O
2
Reaction with dichloroacetonitrile.
Δ
Br2InO
R1
Br2InO
R1
CN
CN
Br
and since we have obtained the corresponding alcohol 6
from this ketone [2a], we attribute this drawback to the
failure of InBr to insert into the carbon–bromine bond of
the indium(III) alkoxide 3 to form the intermediate 4.
The stereoselectivity of the process also depends on the
primary coupling. In general, the Z/E diastereomeric ratios
determined for compounds 5 follow closely the syn/anti
ratio determined preliminarily for the alcohols 6 [2a].
Scheme 3 describes the direct relationship between stereo-
isomers 5 and the diastereoisomers 3.
It is also possible to carry out the coupling followed by
the elimination reactions with dichloroacetonitrile with
comparable efficiency (Table 1, entries c and e), although
in these cases significative enhancement of the stereoselec-
tivity towards the E-isomer was observed.
In summary, this work shows how to use indium mono-
halides to produce reactive organoindium(III) species from
gem-dihalogenoalkanes, capable of useful organic
sequenced transformations. It establishes an attractive
alternative to the Boord reaction to extrude oxygen from
carbonyl compounds to generate olefins [5], in which the
key step is the ejection of the b-related bromine and oxygen
atoms of the 2-bromo-3-alkoxynitrile intermediates 3. Fur-
ther, the work offers a single step, one-pot, new protocol
for preparing 3-organyl-2-alkenenitriles, 5. Compounds 5
have been prepared by dehydration of b-hydroxynitriles
promoted by strong bases [6]. The present method, which
is conducted under neutral conditions, enhances signifi-
cantly the formation of the Z-isomers in the resulting mix-
tures. Improvements on the stereoselectivity of the
reaction, as dictated by the proposed mechanism, depend
on the presence of a bulky substituent attached to the
dihalogenonitrile, since it is expected that steric hindrance
between this group and the organyl aldehyde substituent
would determine the reaction stereoselectivity.
3
R2
InBr2
R2
4
H+
InBr
HO
R1
HO
R1
CN
H
CN
Br
O
1. InBr
2. H+
R1
R2
Et3N
CN
8
7
6
R2
R2
Scheme 2. Indium(I) bromide-promoted sequenced reactions between
dibromoacetonitrile and carbonyl compounds.
aldehydes (see below), is equivalent to a Boord-type elimi-
nation of b-related bromine and oxygen atoms of the alk-
oxide 3 [4]. This reaction is very sensitive to moisture,
which is in fact responsible for the alcohol side products
6 and 7. As we have demonstrated, hydrolysis of alkoxide
3 gave 2-bromo-3-hydroxynitriles, 6 [2a]. The hydroxynitr-
iles 7 are derived from 6 by reduction of their carbon–
bromine bond promoted by InBr. Finally, compounds 6
are also easily transformed in the epoxides 8 [2a].
Of course, the conversion of the aldehyde 2 into the alk-
enenitrile 5 is more conveniently achieved by the direct
action of two equivalents of InBr on a mixture containing
equivalent quantities of the aldehyde 2 and dibromoaceto-
nitrile. The results of these experiments are depicted in
Table 1.
The efficiency of the reaction is governed by the primary
coupling between the organoindium 1 and the carbonyl
compounds leading to the alkoxide 3. We have determined
in previous studies that the best yields for this coupling
occurred with aromatic aldehydes containing electron with-
drawing groups [2a], which again offered superior yields of
the alkenenitriles 5. The reaction failed for acetophenone;

C. Peppe et al. / Journal of Organometallic Chemistry 691 (2006) 2335–2339
2337
3. Experimental
O
O
NC
NC
InBr2
InBr2
InBr
InBr
H
CHBr2CN + RCHO
H
R
H
H
Br
R
3.1. The intermolecular coupling of dibromoacetonitrile with
aldehydes/Boord elimination of bromine and oxygen of
b-bromo alkoxides for preparation of 3-organyl-2-
alkenenitriles
Br
Reduced Steric Hindrance
Steric Hindrance ( R and CN groups)
R
R
OInBr2
OInBr2
H+
A Schlenk test tube equipped with a condenser, truly
dried under high vacuum, was charged with 2 mL of dry
(sodium) THF, 195 mg (1.0 mmol) of the red solid InBr
and dibromoacetonitrile (0.5 mmol). To this mixture was
added 0.5 mmol of the aldehyde and the reaction was kept
under reflux for l4 h. At the end of this period, the reaction
was quenched with water. The organics were extracted with
ethyl acetate. The extract was dried (Na2SO4) and evapo-
rated to dryness. The alkenenitriles 5 were separated as a
mixture of isomers by column chromatography with hex-
anes. The diastereomeric Z:E ratios were determined by
1H NMR spectroscopy. TLC (in hexanes) allowed separa-
tion of the pure Z and E diastereoisomers. The only excep-
tion was the alkenenitriles derived from decanal, 5j which
could not be separated. Yields of reactions and diastereo-
meric ratios are given in Table 1.
H+
H
HO
R
H
H
H
H
OH
H
NC
NC
R
Br
CN
anti-6
( favoured product)
Br
H
H
CN
syn-6
Br
syn-3
Br
anti-3
InBr
InBr
Br2InO
H
OInBr2
H
R
H
R
NC
NC
H
InBr2
InBr2
H
R
R
H
H
H
OInBr2
OInBr2
NC
NC
InBr2
InBr2
H
H
R
H
R
H
NC
(Z) 5
(favoured product)
NC
(E) 5
3.2. The preparation of 3-(40-chlorophenyl)-3-hydroxy-
propanenitrile 7c
Scheme 3. Proposed reaction pathway of the indium(I) bromide-pro-
moted sequenced reactions between dibromoacetonitrile and carbonyl
compounds.
2-Bromo-3-(40-chlorophenyl)-3-hydroxy-propanenitrile,
6c was prepared according to the literature [2a]. Compound
6c (1 mmol) was dissolved in 3 mL of THF:H2O (2:1), at
room temperature. To this solution was added InBr
(1.2 mmol). After the dissolution of the red solid InBr, the
reaction was stirred for 6 h, quenched with water, and then
extracted with ethyl acetate. The product 7c was purified by
column chromatography on silica gel with hexane:acetate
4:1 (v/v). This procedure gave 7c in 70% of yield.
To this end, we would like to point out the differences
between the present results with the very similar reaction
between a,a-dibromoacetonitrile and benzaldehyde promoted
by indium metal, which leads to a low yield of a complex
mixture of products containing 2-cyano-phenyl-oxyrane
(34%, cis:trans = 2:1), 2,2-dibromo-3-hydroxy-3-phenyl-
propanenitrile (13%), 2-bromo-3-phenylpropenenitrile
(4%) and 3-phenylpropenenitrile (4%) [7]. The nature of
the products suggests that the reaction between metallic
indium and CHBr2CN produces two distinct organoindium
compounds carrying the organometallic units In–CBr2CN,
with the metal acting as a reducing agent and In–CHBrCN,
produced by an oxidative insertion of the metal into one of
the carbon–bromine bonds of CHBr2CN. The organoindium
product containing the In–CHBrCN unit is responsible
for the generation of 2-cyano-phenyl-oxyrane and 3-phenyl-
propenenitrile, while the product containing the
In–CBr2CN unit gives 2,2-dibromo-3-hydroxy-3-phenyl-
propanenitrile and 2-bromo-3-phenylpropenenitrile. The
chemioselectivity obtained from reactions promoted by
InBr allows the selective production of the a-bromo-b-
hydroxynitriles 6, the oxiranes 8, the b-hydroxynitriles 7,
and/or the alkenenitriles 5 via the organoindium intermedi-
ate 1; and as also pointed in our earlier studies [3,8], the use
of indium monobromide as the promoter of organic reac-
tions may lead to different products than those obtained
from reactions mediated by metallic indium.
3.3. Spectroscopic studies
The structures of the alkenenitriles 5a–k and of the alco-
hol 7c were determined by NMR (1H and 13C) spectros-
copy and mass spectrometry. The spectroscopic data are
summarized below.
(Z)-Cinnamonitrile, 5a [6a,9–11]: yellowish oil; 1H
NMR (CDCl3): d = 5.34 (d, 3J = 12.1 Hz, 1H), 7.02 (d,
3J = 12.1 Hz, 1H), 7.34 (m, 3H), 7.69 (m, 2H); 13C NMR
(CDCl3): d = 95.10, 117.29, 128.92, 129.00, 130.96,
133.59, 148.68; 13C NMR (DEPT-135): d = 95.10, 128.92,
129.00, 130.96, 148.68.
1
(E)-Cinnamonitrile, 5a [6a,9,11,12]: yellowish oil; H
3
NMR (CDCl3): d = 5.88 (d, J = 16.6 Hz, 1H), 7.43 (m,
6H); 13C NMR (CDCl3): d = 96.38, 118.09, 127.34,
129.11, 131.20, 133.55, 150.56; 13C NMR (DEPT-135):
d = 96.38, 127.34, 129.11, 131.20, 150.56.
(Z)-2-Chlorocinnamonitrile, 5b [6a,9–11]: yellowish oil;
1H NMR (CDCl3): d = 5.54 (d, 3J = 12.0 Hz, 1H), 7.31 (m,
3
3H), 7.47 (d, J = 12.0 Hz, 1H), 7.99 (m, 1H); 13C NMR

2338
C. Peppe et al. / Journal of Organometallic Chemistry 691 (2006) 2335–2339
(CDCl3): d = 98.11, 116.48, 127.18, 128.94, 129.84, 131.68,
134.32, 145.20, 145.23; MS (70 eV, EI, for 35Cl): m/z
(%):163 (M, 40), 128 (100), 101 (22), 75 (35).
(E)-2-Chlorocinnamonitrile, 5b [6a,9,11]: yellowish oil;
1H NMR (CDCl3): d = 5.83 (d, 3J = 16.7 Hz, 1H), 7.35 (m,
4H), 7.76 (d, 3J = 16.7 Hz, 1H); 13C NMR (CDCl3):
d = 98.91, 117.62, 126.82, 127.27, 130.33, 131.68, 131.94,
134.43, 146.50; MS (70 eV, EI, for 35Cl): m/z (%): 163
(M, 94), 128 (100), 101 (48), 75 (41).
(Z)-4-Chlorocinnamonitrile, 5c [6a,10,11]: colorless
solid, m.p. >300 °C; 1H NMR (CDCl3): d = 5.40 (d,
3J = 12.0 Hz, 1H), 7.01 (d, 3J = 12.0 Hz, 1H), 7.34 (m,
2H), 7.67 (m, 2H); 13C NMR (CDCl3): d = 95.71, 116.97,
129.21, 130.22, 131.98, 136.96, 147.21; MS (70 eV, EI, for
35Cl): m/z (%): 163 (M, 100), 128 (98), 101 (31).
(E)-4-Methylcinnamonitrile, 5f [6a,9]: yellowish oil;
1H NMR (CDCl3): d = 2.30 (s, 3H), 5.73 (d,
3J = 16.6 Hz, 1H), 7.21 (m, 5H); 13C NMR (CDCl3):
d = 21.43, 94.98, 118.32, 127.25, 129.74, 130.75, 141.74,
150.42; 13C NMR (DEPT-135): d = 21.43, 94.98, 127.25,
129.74, 150.42; MS (70 eV, EI): m/z (%): 143 (M, 100),
115 (77), 89 (21).
(Z)-2-Methoxycinnamonitrile, 5g [10,13]: yellowish oil;
3
1H NMR (CDCl3): d = 3.77 (s, 3H), 5.33 (d, J = 12.2 Hz,
1H), 6.90 (m, 2H), 7.32 (m, 1H), 7.49 (d, 3J = 12.2 Hz, 1H)
8.00 (d, 1H); 13C NMR (CDCl3): d = 55.53, 94.65, 110.84,
117.55, 120.72, 122.71, 128.28, 132.26, 143.63, 157.46.
(E)-2-Methoxycinnamonitrile, 5g: yellowish oil; 1H
NMR (CDCl3): d = 3.82 (s, 3H), 5.98 (d, 3J = 16.7 Hz,
3
1H), 6.88 (m, 2H), 7.31 (m, 2H), 7.55 (d, J = 16.7 Hz,
(E)-4-Chlorocinnamonitrile, 5c [6a,9–11]: colorless
1H); 13C NMR (CDCl3): d = 55.52, 96.97, 111.29, 118.93,
120.81, 122.56, 128.89, 132.27, 146.39, 158.22; MS (70 eV,
EI): m/z (%): 159 (M, 75), 131 (100), 116 (53).
1
solid, m.p. 84.1–86.2 °C; H NMR (CDCl3): d = 5.79 (d,
3J = 16.6 Hz, 1H), 7.27 (d, 3J = 16.6 Hz, 1H), 7.32 (s,
4H); 13C NMR (CDCl3): d = 97.01, 117.76, 128.51,
129.44, 131.98, 137.30, 149.10; 13C NMR (DEPT-135)
d = 97.01, 128.51, 129.44, 149.10; MS (70 eV, EI, for
35Cl): m/z (%): 163 (M, 100), 128 (99), 114(10), 101 (37).
(Z)-2-Bromocinnamonitrile, 5d [11,13]: greenish oil; 1H
(Z)-4-Methoxycinnamonitrile, 5h [6a,9]: yellowish oil;
1H NMR (CDCl3): d = 3.78 (s, 3H), 5.22 (d,
3J = 12.0 Hz, 1H), 6.87 (d, 2H), 6.96 (d, 3J = 12.0 Hz,
1H), 7.72 (d, 2H); 13C NMR (CDCl3): d = 55.56, 91.93,
114.52, 117.95, 126.56, 130.93, 148.00, 161.66; 13C NMR
(DEPT-135): d = 55.56, 91.93, 114.52, 130.93, 148.00; MS
(70 eV, EI): m/z (%): 159 (M, 100), 144 (39), 130 (10),
116 (56), 89 (51).
3
NMR (CDCl3): d = 5.50 (d, J = 12.0 Hz, 1H), 7.36 (m,
4H), 7.94 (d, 1H); 13C NMR (CDCl3): d = 98.25, 116.31,
124.43, 127.75, 129.18, 131.73, 133.07, 133.42, 147.72;
MS (70 eV, EI, for 79Br): m/z (%): 207 (M, 77), 180 (7),
128 (100), 101 (62), 75 (38).
(E)-4-Methoxycinnamonitrile, 5h [6a,9,12]: yellowish
oil; 1H NMR (CDCl3): d = 3.77 (s, 3H), 5.64 (d,
3J = 16.5 Hz, 1H), 6.84 (d, 2H), 7.27 (m, 3H); 13C NMR
(CDCl3): d = 55.43, 93.40, 114.52, 118.64, 126.37, 129.05,
150.00, 162.06; 13C NMR (DEPT-135): d = 55.43, 93.40,
114.52, 129.05, 150.00; MS (70 eV, EI): m/z (%): 159 (M,
100), 144 (41), 129 (10), 116 (57), 89 (51).
(E)-2-Bromocinnamonitrile, 5d [11]: greenish oil; 1H
3
NMR (CDCl3): d = 5.78 (d, J = 16.6 Hz, 1H), 7.24 (m,
2H), 7.49 (m, 2H), 7.70 (d,3J = 16.6 Hz, 1H); 13C NMR
(CDCl3): d = 98.96, 117.53, 124.66, 126.89, 127.85,
132.06, 133.32, 133.50, 148.92; 13C NMR (DEPT)
d = 98.96, 126.89, 127.85, 132.06, 133.50, 148.92; MS
(70 eV, EI, for 79Br): m/z (%): 207 (M, 77), 180(8), 128
(100), 101 (62), 75 (38).
(Z)-Non-2-enenitrile, 5i: colorless oil; 1H NMR
(CDCl3): d = 0.81 (t, 3J = 7.1 Hz, 3H), 1.15–1.43 (m,
3
3
8H), 2.34 (q, br, J = 7.7 Hz, 2H), 5.22 (dt, J = 11.0 Hz,
3J = 1.2 Hz, 1H), 6.40 (dt, 3J = 11.0 Hz, 3J = 7.7 Hz, 1
H); 13C NMR (CDCl3): d = 13.96, 22.47, 28.18, 28.66,
31.45, 31.85, 99.42, 116.02, 155.23; MS (70 eV, EI): m/z
(%): 137 (M, 2), 136 (14), 122 (27), 108 (43), 94 (46), 80
(40), 67 (100), 55 (61).
(Z)-4-Bromocinnamonitrile, 5e [6a]: colorless solid,
m.p. >300 °C; 1H NMR (CDCl3): d = 5.42 (d,
3
3J = 12.0 Hz, 1H), 7.00 (d, J = 12.0 Hz, 1 H), 7.56 (m,
4H); 13C NMR (CDCl3): d = 95.84, 116.95, 125.36,
130.35, 132.18, 133.37, 147.30; 13C NMR (DEPT-135):
95.84, 130.35, 132.18, 147.30; MS (70 eV, EI, for 79Br):
m/z (%): 207 (M, 78), 180 (7), 128 (100), 101 (43), 75 (28).
(E)-4-Bromocinnamonitrile, 5e [6a]: colorless solid,
m.p. 105.0–105.8 °C; 1H NMR (CDCl3): d = 5.77 (d,
3J = 16.7 Hz, 1H), 7.25 (m, 3H), 7.48 (m, 2H); 13C NMR
(CDCl3): d = 97.08, 117.75, 125.60, 128.66, 132.34,
132.36, 149.17; 13C NMR (DEPT-135): d = 97.08, 128.66,
132.34, 149.17; MS (70 eV, EI, for 79Br): m/z (%): 207
(M, 79), 180(6), 128 (100), 101 (44), 75 (30).
(E)-Non-2-enenitrile, 5i [14]: colorless oil; 1H NMR
3
(CDCl3): d = 0.81 (t, J = 6.9 Hz, 3H), 1.13-1.40 (m, 8H),
2.13 (q, br, 3J = 7.0 Hz, 2H), 5.23 (dt, 3J = 16.4 Hz,
3J = 1.4 Hz, 1H), 6.64 (dt, 3J = 16.4 Hz, 3J = 7.0 Hz,
1H); 13C NMR (CDCl3): d = 13.95, 22.45, 27.58, 28.60,
31.44, 33.29, 99.64, 117.54, 156.12; MS (70 eV, EI): m/z
(%): 137 (M, 2), 136 (17), 122 (34), 108 (57), 94 (52), 80
(35), 69 (100), 55 (86).
(Z + E)-Dodec-2-enenitrile, 5j (mixture Z:E = 4:3): col-
orless oil; 1H NMR (CDCl3): d = 0.82 (t, 3J = 6.7 Hz,
21H), 1.20 (s, br, 98H), 2.14 (q, br, 3J = 7.0 Hz, 6H),
2.35 (q, br, 3J = 7.6 Hz, 8H), 5.23 (dt, 3J = 10.8 Hz,
3J = 1.2 Hz, 4H), 5.25 (dt, 3J = 16.3 Hz, 3J = 1.6 Hz,
3H), 6.40 (dt, 3J = 10.8 Hz, 3J = 7.6 Hz, 4H), 6.64 (dt,
1
(Z)-4-Methylcinnamonitrile, 5f [6a]: yellowish oil; H
NMR (CDCl3): d = 2.31 (s, 3H), 5.29 (d, 3J = 12.2 Hz,
1H), 7.00 (d, 3J = 12.2 Hz, 1H), 7.16 (d, 2H), 7.63 (d,
2H); 13C NMR (CDCl3): d = 21.48, 93.70, 117.55, 129.00,
129.56, 130.94, 141.51, 148.55; 13C NMR (DEPT-135):
d = 21.48, 93.70, 129.00, 129.56, 148.55; MS (70 eV, EI):
m/z (%): 143 (M, 100), 115 (83), 89 (25), 63 (26).
3
3J = 16.3 Hz, J = 6.9 Hz, 3 H); MS (70 eV, EI): m/z (%
E,Z): 178 (M, 10, 10), 164 (18, 16), 150 (56, 74), 136 (68,

C. Peppe et al. / Journal of Organometallic Chemistry 691 (2006) 2335–2339
2339
98), 122 (67, 100), 108 (50, 40), 94 (79, 63), 80 (100, 64), 67
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(96, 85), 54 (83, 94).
[1] C. Peppe, Curr. Org. Synth. 1 (2004) 227.
5-Phenyl-penta-2(Z),4(E)dienenitrile, 5k [10]: yellow
oil; 1H NMR (CDCl3): d = 5.16 (d, 3J = 10.4 Hz, 1H),
6.80–7.45 (m, 8H); 13C NMR (CDCl3): d = 96.44, 116.63,
124.04, 127.52, 128.83, 129.65, 135.19, 141.63, 149.19; 13C
NMR (DEPT-135): d = 96.44, 124.04, 127.52, 128.83,
129.65, 141.63, 149.19; MS (70 eV, EI): m/z (%): 154
(Mꢀ1, 100), 141 (88), 115 (97), 77 (48).
´
[2] (a) J.A. Nobrega, S.M.C. Gonc¸alves, C. Peppe, Tetrahedron Lett. 41
(2000) 5779;
´
(b) J.A. Nobrega, S.M.C. Gonc¸alves, C. Peppe, Tetrahedron Lett. 42
(2001) 4745.
[3] C. Peppe, R.P. dasChagas, Synlett (2004) 1187.
[4] J. March, Advanced Organic Chemistry. Reactions, Mechanisms
and Structure, fourth ed., Wiley, New York, 1992, pp. 1034–
1036.
[5] For an earlier example of coupling between an a,a-dibroalkanenitrile
and an aldehyde, followed by a Boord elimination mediated by zinc,
see: D.R. White, Tetrahedron Lett. 21 (1976) 1753.
[6] (a) From KOH/acetonitrile, see: S.A. DiBiase, B.A. Lipisko, A.
Haag, R.A. Wolak, G.W. Gokel, J. Org. Chem. 44 (1979) 4640;
(b) , From MeMgCl, see: F.F. Fleming, J. Org. Chem. 67 (2002)
3668.
[7] S. Araki, T. Hirashita, K. Shimizu, T. Ikeda, Y. Butsugan, Tetrahe-
dron 52 (1996) 2803.
[8] C. Peppe, R.P. das Chagas, Synlett (2006) in press.
[9] X. Huang, L. Xie, H. Wu, J. Org. Chem. 53 (1988) 4862.
[10] S. Kojima, T. Fukuzaki, A. Yamakawa, U. Murai, Org. Lett. 6
(2004) 3917.
5-Phenyl-penta-2(E),4(E)dienenitrile; 5k: yellow oil; 1H
3
NMR (CDCl3): d = 5.33 (d, J = 15.7 Hz, 1H), 6.72–7.35
(m, 8H); 13C NMR (CDCl3): d = 98.14, 118.29, 125.33,
127.32, 128.83, 129.56, 135.15, 141.26, 150.23; 13C NMR
(DEPT-135): d = 98.14, 125.33, 127.32, 128.83, 129.56,
141.26, 150.23; MS (70 eV, EI): m/z (%): 155(100), 141
(72), 115(87), 77(41).
3-(40-Chlorophenyl)-3-hydroxypropanenitrile, 7c [15]:
1
3
yellowish oil; H NMR (CDCl3): d = 2.65 (d, J = 6.1 Hz,
3
2H), 2.69 (s, br, 1H), 4.92 (t, J = 6.1 Hz, 1H), 7.27 (m,
4H); 13C NMR (CDCl3): d = 29.91, 69.20, 117.09, 126.91,
128.99, 134.46, 139.46.
[11] F. Texier-Boullet, A. Foucaud, Synthesis (1979) 884.
[12] A. Loupy, K. Sogadji, J. Seyden-Penne, Synthesis (1977) 126.
[13] C.N. Robinson, J.L. Horton, D.O. Foshee, J.W. Jones, S.H.
Hanissian, C.D. Slater, J. Org. Chem. 51 (1986) 3535.
[14] M. Rottla¨nder, L. Boymond, G. Cahiez, P. Knochel, J. Org. Chem.
64 (1999) 1080.
Acknowledgement
P.D.M. and R.P.D thank CNPq for the award of
scholarships.
[15] Y.-Z. Huang, Y. Liao, J. Org. Chem. 56 (1991) 1381.