Phenyltelluroacrylonitriles and phenylselenoacrylonitriles as precursors of (Z)-α-phenylseleno-α,β-unsaturated aldehydes, β-amino-α-phenylselenonitriles and Diels-Alder adducts

Article abstract of DOI:10.1016/S0040-4020(01)00580-4

Reaction of cyanomethylphosphonate with aryl selenenyl (or tellurenyl) halides and aldehydes, under basic conditions, provides α-phenylseleno or α-phenyltelluro acrylonitriles in good yields. Reaction of the α-phenylseleno acrylonitriles with dienes furnishes the corresponding adducts while reaction with amines furnishes α-phenylseleno-β-amino nitriles. Selective reduction of the cyano group with DIBAL-H results in the α-phenylseleno-α,β-unsaturated aldehydes.

Full text of DOI:10.1016/S0040-4020(01)00580-4

TETRAHEDRON
Pergamon
Tetrahedron 57 *2001) 5953±5959
Phenyltelluroacrylonitriles and phenylselenoacrylonitriles as
precursors of ꢀZ)-a-phenylseleno-a,b-unsaturated aldehydes,
b-amino-a-phenylselenonitriles and Diels±Alder adducts
Claudio C. Silveira,a,p Gelson Perin,a Antonio L. Braga,a Miguel J. Dabdoubb
and Raquel G. Jacobc
a
Â
Departamento de Quõmica, Universidade Federal de Santa Maria, C.P. 5001, 97105-970 Santa Maria, RS, Brazil
b
Â
Departamento de Quõmica, FFCLRP, Universidade de SaÄo Paulo, RibeiraÄo Preto, SP, Brazil
c
 Â
Departamento de Biologia e Quõmica, UNIJUI, Ijuõ, RS, Brazil
Received 5 March 2001; accepted 22 May 2001
AbstractÐReaction of cyanomethylphosphonate with aryl selenenyl *or tellurenyl) halides and aldehydes, under basic conditions, provides
a-phenylseleno or a-phenyltelluro acrylonitriles in good yields. Reaction of the a-phenylseleno acrylonitriles with dienes furnishes the
corresponding adducts while reaction with amines furnishes a-phenylseleno-b-amino nitriles. Selective reduction of the cyano group with
DIBAL-H results in the a-phenylseleno-a,b-unsaturated aldehydes. q 2001 Elsevier Science Ltd. All rights reserved.
1. Introduction
a-Cyano substituted vinylic sul®des have been prepared by
several different routes.7 However, the preparation of
a-phenylselenoacrylonitriles is scarcely known8 and no
methods to the corresponding a-phenyltelluroacrylonitriles
were described up to date. To the best of our knowledge, the
only method reported for preparing the a-phenylseleno-
acrylonitriles involves the addition of benzeneselenenyl
chloride or bromide to cyano ole®ns leading to a-seleno
adducts, which are subjected to in situ dehydrohalogenation.6,8
Vinylic sul®des a-substituted by strong electron withdraw-
ing groups have been synthetically used as potent Michael
acceptors,1 in a variety of cycloaddition reactions2 and in
studies as precursors of extended enolates.3 The selenium
analogs have been used as dienophiles in Diels±Alder
reactions,4 as Michael acceptors5 and in the synthesis of
2,3-dihydroselenophenes and butadienes.6
Scheme 1.
Keywords: Wittig reactions; aldehydes; phenylseleno or phenyltelluroacrylonitriles; a-phenylseleno-b-amino nitriles.
Corresponding author. Fax: 155-55-220-8754; e-mail: silveira@quimica.ufsm.br
p
0040±4020/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020*01)00580-4

5954
C. C. Silveira et al. / Tetrahedron 5732001) 5953±5959
Table 1. a-Phenylseleno and a-phenyltelluro acrylonitriles obtained
Entry
1
R
Products
Reaction time *h)
1.5
Yield *%)
925.0:1
Ratio *Z/E)
*CH3)2CH
2CH
3CH2CH2
1.5
1.5
1.5
1.5
0.5
0.5
80
81
58
81
86
78
5.2:1
2.6:1
±
3
4
5
6
7
CH3
H
CH3CH2CHCH
2.7:1
3.0:1
6.8:1
C6H5
C6H5CHCH
8
9
CH3CH2CH2
1.5
1.5
93
81
5.6:1
4.5:1
CH3*CH2)2CH2
10
11
*CH3)2CH
1.5
1.5
78
23
4.5:1
±
H
However, it is important to note that the chemical reactivity
of this kind of compounds remains almost unexplored. On
the basis of the described methods, one can state that the
preparation of 2-*organylseleno)propenenitriles is more
dif®cult than the preparation of the corresponding thio
analogues.
2. Results and discussion
2.1. Preparation of a-phenylseleno or a-phenyltelluro
acrylonitriles
Cyanomethylphosphonate 1 is easily available on a large
scale by the Arbuzov reaction of triethylphosphite with
chloromethyl acetonitrile10 and it is a very useful inter-
mediate in a variety of important transformations. Treat-
ment of 1 with LDA generated the lithiated species 2
which, upon reaction with benzenetellurenyl bromide or
benzeneselenenyl chloride in THF, afforded the a-phenyl-
chalcogeno*cyano)phosphonate intermediates 3 as depicted
in Scheme 1. Intermediate 3 was easily transformed into the
desired product 4 or 5 in a one-pot process *without
isolation) using LDA in excess followed by reaction with
aldehydes. In most cases, good to excellent yields *78±93%)
were obtained by using aromatic and aliphatic aldehydes.
We have recently described practical methodologies for the
preparation of vinyl chalcogenides based on Wittig and
Wittig±Horner reactions.9 Due to our continuous interest
on the synthesis of functionalized vinylic chalcogenides,
we report here the application of the Horner±Wittig reaction
to make easier the synthesis of a-phenylseleno acrylo-
nitriles and for the ®rst synthesis of phenyltelluro acrylo-
nitriles. Studies on the chemical reactivity of a-phenyl-
seleno acrylonitriles in reactions with DIBAL-H, with
amines and in a Diels±Alder-type reaction are also
described.

C. C. Silveira et al. / Tetrahedron 5732001) 5953±5959
Table 2. Products obtained from a-phenyl selenoacrylonitriles
Entry Reagent Products
5955
Yield *%)
Ratio *Z/E)
However, the reactions with formaldehyde gave lower
yields, particularly for the tellurium derivative case *entry
11, Table 1).
unstable under the reaction employed. However, this is
the ®rst method to this potentially very useful, new class
of tellurium compounds. It is noteworthy that by our method
it was possible to prepare the simplest and new phenyl-
seleno and phenyltelluro acrylonitriles 4d and 5d derived
from formaldehyde, albeit in only 58 and 23% yield, respec-
tively, as a consequence of low stability of these products.
The sulfenylation of the diethyl cyanomethylphosphonate
anion 2 with phenylsulfenyl chloride during the synthesis
of a-phenylsulfenylacrylonitriles by a Horner±Emmons
reaction modi®cation, gave low yields *37±47%). All
efforts to generate exclusively the intermediate
*EtO)2POCH*SPh)CN *analogous to 3) using 1:1 molar
ratio of PhSCl and the anion 2 led to *EtO)2POC*SPh)2CN
as the major product.11
Although most experiments were performed on a 1.0 mmol
scale, these reactions can also be performed successfully on
higher scales *up to 10 mmol) with comparable yields.
Concerning the stereochemistry of the obtained ole®ns, we
usually observed the formation of Z and E isomer mixtures.
In the case of aliphatic derivatives, the Z and E isomers
ratios were directly obtained by 1H NMR analysis
*400 MHz). However, for 4f and g products, this ratio
By contrast, we observed that phenyltellurenyl bromide
excess was required to afford 5 in good yields. For example,
intermediate 2 reacts with equimolar amounts of PhTeBr,
followed by the addition of n-butyraldehyde, providing 5a
in 47% yield, while the yield increases to 67 and 93% by
using 1.5 and 2.0 equiv. of the PhTeBr, respectively. On the
other hand, using an excess of anion 2 *2.0 equiv.), the
desired vinylic product was not formed. It was also observed
that an excess of phenyl selenenyl chloride *1.5 equiv.) was
required to afford good yields of 4. The excess of these
easily accessible reagents can be recovered at the puri®-
cation step in the PhSeSePh or PhTeTePh form.
1
could not be determined directly by H NMR, because the
vinylic proton signals overlaped with the aromatic hydro-
gens. For 4f *reaction with benzaldehyde), the ratio was
obtained by the analysis of their 13C NMR spectra. The
presence of Z and E isomers could be easily con®rmed
since two peaks relative to the CN group appeared at d
97.9 and 104.0. The same ratio was observed for the alde-
hyde obtained by the reduction of the CN moiety with
DIBAL-H *vide infra).
The method described here exhibits good generality to the
phenylselenoacrylonitriles and it is successful with aromatic
and aliphatic aldehydes, while for phenyltelluro acrylo-
nitriles, the reaction was possible only with aliphatic alde-
hydes and the products from aromatic derivatives are
For product 4g *entry 7, Table 1), the Z/E isomers *6.8:1)
were easily separated by column chromatography and the
major isomer was shown to have the Z-con®guration by
X-ray crystallography.12

5956
C. C. Silveira et al. / Tetrahedron 5732001) 5953±5959
Scheme 2.
An alternative experimental condition employing BF3´OEt2
*2.3 equiv.) was applied in one experiment between n-butyr-
aldehyde *1.2equiv.) and the a-phenylseleno-a-cyano-
methylphosphonate of type 3. In this case, the proportion
of the Z-isomer was increased *from 5.2:1 to 10:1), but the
yield of 4b was slightly lower *72% isolated yield). The
effect of BF3´OEt2 on the stereochemistry and the scope of
the observed effect deserve further investigation.
Scheme 4.
NOESY experiment and by the 13C NMR spectra where
single peaks for all carbons were observed.
2.3. Preparation of a-phenylseleno-b-amino nitriles
2.2. Selective reduction of the nitrile moiety
The a-phenylseleno-b-amino esters have attracted con-
siderable attention due to their utility as precursors of
modi®ed b-amino esters,16 oligopeptides17 and a-phenyl-
seleno-b-lactams.18 The presence of the organoselenium
functional group provides an entry into radical chemis-
try.16,17,19
a-Phenylseleno-a,b-unsaturated aldehydes have recently
been prepared by the reaction of 1-lithio-2-ethoxy vinyl
selenides with aldehydes and ketones, followed by acid-
catalyzed dehydration.13 Some other methods were also
described for the preparation of this class of compounds.14a,b
They have been used to access selenobutadienes15a and in a
Diels±Alder-type reaction.15b,14b
The addition of the amines to ole®ns bearing an electron-
withdrawing substituent has been known for a long time.
The addition takes place probably involving a typical 1,4-
addition mechanism. In this way, we decided to perform the
reaction of nitrile 4d with two different amines. Performing
the reaction with an ethanolic solution of *1R,2S)-*2)-
ephedrine, the product 8 was easily obtained in 67% isolated
yield, as a 1:1 mixture of diastereoisomers. In the case of
reaction with morpholine, this amine was added neat to the
nitrile 4d at room temperature and the corresponding
product was isolated in 82% yield. This reaction furnishes
an easy access to the highly functionalized nitriles 8 and 9
directly from the readily available a-phenylseleno acrylo-
nitrile 4d *Scheme 3; Table 2, entries 3 and 4).
In the present work, we decided to study the selectivity on
the reduction of the CN moiety from a-phenylseleno acrylo-
nitriles. For this purpose, some of the obtained a-phenyl-
seleno acrylonitriles were reacted with DIBAL-H at 2788C,
warming up the solution slowly to room temperature and
keeping the reaction at this temperature for 1 h, followed by
aqueous quenching. It was observed that the use of 2equiv.
of DIBAL-H was crucial to afford good yields of 6 or 7.
Concerning to the stereochemistry of the obtained products,
in the case of the a-phenylselenocinnamaldehyde 6 *entry 1,
Table 2), we observed the formation of Z and E isomers
mixture in a 3.5:1 ratio. The Z and E isomers were easily
separable by column chromatography *entry 1, Table 2) and
should be noted that the reaction occurred with nearly total
retention of con®guration since the starting material used
*4f) was a mixture of Z and E isomers in a ca. 3:1 ratio *entry
6, Table 1) *Scheme 2).
2.4. Study on the reactivity of 4d in a Diels±Alder
reaction
The Diels±Alder reaction is one of the most useful and
powerful tools in preparative organic chemistry.20 With
this in mind, we decided to perform studies on the reaction
of a-phenylseleno a,b-unsaturated esters as dienophiles in
Diels±Alder reactions with commercially available dienes.
For our study, we decided to use the simplest reagent of this
class of compounds *4d) *Scheme 4).
In the other example studied, the Z-isomer of compound 4g
was employed furnishing the corresponding a-phenyl-
seleno-a,b,g,d-unsaturated aldehyde 7 in 55% yield *entry
2, Table 2). This reaction occurred with complete retention
of the Z-con®guration as con®rmed by 1H NMR *400 MHz),
Scheme 3.

C. C. Silveira et al. / Tetrahedron 5732001) 5953±5959
5957
Compound 4d was reacted with a small excess of isoprene
and 1.4 equiv. of the EtAlCl2, using dichloromethane
*4 mL) as solvent. This reaction proceeded regioselectively
to give 10 in 69% isolated yield. The formation of the para
isomer was con®rmed by a NOESY NMR study and no
other regioisomer was detected.
100.0), 155 *31.7), 94 *25.7), 77 *87.1); IR *®lm, cm21):
2210 *CN). H NMR *300 MHz, CDCl3) d *Z1E) 1.02±
1
1.10 *m, 6H); 2.76±3.05 *m, 1H); 6.64 *Z) and 6.65 *E)
*2d, Jˆ9.9 Hz, 1H); 7.20±7.37 *m, 3H); 7.42±7.60 *m,
2H); 13C NMR *50 MHz, CDCl3) d 21.3, 21.6, 31.9, 33.5,
97.9, 101.4, 115.8, 117.3, 127.2, 127.9, 128.6, 128.8, 129.6,
133.4, 134.2, 160.2, 163.6. Anal. calcd for C12H13NSe: C,
57.61; H, 5.24. Found: C, 57.91; H, 5.14.
The reaction of 4d with cyclopentadiene, under the con-
ditions described above, showed a low stereoselectivity,
and the adduct 11 was obtained in a 4.5:1 *endo/exo)
ratio, in 73% yield. The preferential formation of the endo
isomer was con®rmed by a NOESY NMR experiment. For
both dienes, the best results were obtained with EtAlCl2 as
the Lewis acid.
4.2.2. ꢀZ1E)-2-Phenylselanyl-hex-2-enenitrile ꢀ4b).
Yield 0.201 g *80%). MS m/z *rel. int.) 251 *M111,
100.0), 157 *66.0), 77 *89.1); IR *®lm, cm21): 2211 *CN).
1H NMR *300 MHz, CDCl3) d *Z1E) 0.88±1.00 *m, 3H);
1.42±1.58 *m, 2H); 2.30±2.45 *m, 2H); 6.79 *Z) and 6.84
*E) *2t, Jˆ7.8 Hz, 1H); 7.25±7.35 *m, 3H); 7.50±7.60 *m,
2H); 13C NMR *50 MHz, CDCl3) d 13.4, 13.6, 21.3, 21.5,
34.1, 35.5, 100.2, 103.7, 115.9, 117.3, 127.2, 127.9, 128.6,
128.8, 129.5, 133.5, 134.1, 154.1, 157.3. Anal. calcd for
C12H13NSe: C, 57.61; H, 5.24. Found: C, 57.82; H, 5.05.
3. Conclusions
We have developed a new and simple methodology to the
synthesis of a-phenylseleno and a-phenyltelluro acrylo-
nitriles and studies on the reactivity of the seleno
compounds by reaction with DIBAL-H, with amines and
with dienes were also described here.
4.2.3. ꢀZ1E)-2-Phenylselanyl-but-2-enenitrile ꢀ4c).8b
Yield 0.180 g *81%). H NMR *200 MHz, CDCl3) d 1.97
1
*E) and 2.03 *Z) *2d, Jˆ7.0 Hz, 3H); 6.83 *Z) and 6.89 *E)
*2q, Jˆ7.0 Hz, 1H); *Z1E) 7.19±7.32*m, 3H); 7.51±7.56
*m, 2H); 13C NMR *50 MHz, CDCl3) d 18.0, 19.1, 100.7,
104.2, 115.6, 117.2, 127.0, 127.6, 128.4, 128.6, 129.4,
133.3, 133.8, 149.5, 152.5.
4. Experimental
4.1. General remarks
4.2.4. 2-Phenylselanyl-acrylonitrile ꢀ4d).8 Yield 0.121 g
*58%). MS m/z *rel. int.) 209 *M1, 56.4), 157 *79.5), 91
*100.0), 77 *75.9), 51 *62.5); IR *®lm, cm21): 2216 *CN).
1H NMR *200 MHz, CDCl3) d 6.06 *d, Jˆ0.8 Hz, 1H); 6.43
*d, Jˆ0.8 Hz, 1H); 7.29±7.40 *m, 3H); 7.52±7.63 *m, 2H);
13C NMR *50 MHz, CDCl3) d 110.6, 116.3, 125.9, 129.3,
129.6, 134.6, 134.9.
1H and 13C NMR spectra of CDCl3 solutions were recorded
with a 200, 300 or a 400 MHz spectrometer as noted.
Chemical shifts are expressed as parts per million *ppm)
down®eld from tetramethylsilane as an internal standard.
Mass spectra *EI) were obtained at 70 eV with a Hewlett
Packard EM/CG HP-5988A spectrometer, infra-red spectra
were acquired on a Perkin±Elmer 1310 spectrometer and
elemental analyses were performed with a Vario EL
Elementar Analysis System. Merck's silica gel *230±400
mesh) was used for ¯ash chromatography. THF was
distilled over sodium/benzophenone immediately before
use.
4.2.5. ꢀ1Z11E,3E)-2-Phenylselanyl-hepta-2,4-dienenitrile
ꢀ4e). Yield 0.213 g *81%). MS m/z *rel. int.) 263 *M111,
25.1), 157 *32.7), 106 *18.9), 77 *100.0); IR *®lm, cm21):
1
2204 *CN). H NMR *300 MHz, CDCl3) d *1Z11E,3E)
0.98±1.10 *m, 3H); 2.15±2.30 *m, 2H); 6.18 *1Z,3E) and
6.28 *1E,3E) *2dt, Jˆ14.9, 6.5 Hz, 1H); 6.45 *1Z,3E) and
6.61 *1E,3E) *2ddt, Jˆ14.9, 10.8, 1.5 Hz, 1H); 7.12*1 Z,3E)
and 7.16 *1E,3E) *2d, Jˆ10.8 Hz, 1H); 7.20±7.40 *m, 3H);
7.50±7.60 *m, 2H); 13C NMR *50 MHz, CDCl3) d 12.5,
25.9, 26.2, 96.6, 98.4, 116.2, 118.4, 126.2, 127.7, 127.9,
128.4, 128.5, 129.4, 133.3, 147.7, 149.0, 149.7, 152.2.
Anal. calcd for C13H13NSe: C, 59.55; H, 5.00. Found: C,
59.46; H, 5.16.
4.2. General procedure for the synthesis of a-phenyl-
seleno and a-phenyltelluro acrylonitriles 4±5
A solution of 1 *0.177 g, 1 mmol) in THF *1 mL) was added
dropwise to a solution of LDA *2.1 mmol) in THF *3 mL) at
2788C under nitrogen. The reaction was stirred at this
temperature for 20 min, then a solution of C6H5SeCl
*0.287 g, 1.5 mmol) in THF *1 mL) or C6H5TeBr
*2mmol) in THF *2mL) was added at 2788C. The tempera-
ture was raised to 08C for 30 min, the aldehyde *1 mmol)
was then added and the stirring continued for 30 min at 08C
and for an additional 30±90 min at rt *see Table 1). The
reaction mixture was treated with water and extracted
with ethyl acetate *3£25 mL). The organic layer was dried
over MgSO4 and the solvent removed in vacuo. The residue
was puri®ed by column chromatography *SiO2) using
hexane/ethyl acetate *99:1) as eluent. Spectral data of 4a±g
and 5a±d are listed below.
4.2.6. ꢀZ1E)-3-Phenyl-2-phenylselanyl-acrylonitrile ꢀ4f).
Yield 0.245 g *86%). MS m/z *rel. int.) 285 *M111, 53.7),
204 *55.9), 157 *29.1), 77 *100.0); IR *®lm, cm21): 2203
*CN). 1H NMR *400 MHz, CDCl3) d *Z1E) 7.35±7.60 *m,
6H); 7.52 *s, 1H); 7.64±7.66 *m, 2H); 7.74±7.77 *m, 2H);
13C NMR *100 MHz, CDCl3) d 97.9, 104.0, 117.2, 117.5,
127.7, 127.8, 128.6, 128.8, 128.9, 129.0, 129.6, 129.6,
129.7, 129.7, 130.1, 130.9, 133.8, 134.1, 134.4, 135.5,
145.8, 150.1. Anal. calcd for C15H11NSe: C, 63.39; H,
3.90. Found: C, 63.36; H, 3.52.
4.2.7. ꢀ1Z,3E)-5-Phenyl-2-phenylselanyl-penta-2,4-diene-
nitrile ꢀ4g). Yield 0.211 g *68%). MS m/z *rel. int.) 311
4.2.1. ꢀZ1E)-4-Methyl-2-phenylselanyl-pent-2-enenitrile
ꢀ4a). Yield 0.230 g *92%). MS m/z *rel. int.) 251 *M111,

5958
C. C. Silveira et al. / Tetrahedron 5732001) 5953±5959
*M111, 78.5), 230 *59.0), 154 *100.0), 127 *86.4), 77
hydride *DIBAL-H) *2.0 mL, 2 mmol, 1.0 M solution in
toluene) was added dropwise to a solution of nitrile 4f
*1.0 mmol) in hexane *10.0 mL) at 2788C under nitrogen.
The temperature was allowed to reach rt for 1 h and stirred
for 30 min at rt. The mixture was poured into aq. NH4Cl
solution and after 20 min, aq. sulfuric acid was added and
the product was extracted with ethyl acetate *3£25 mL).
The organic layer was dried over MgSO4 and the solvent
removed in vacuo. The residue was puri®ed by column
chromatography over silica gel and eluted with hexane/
ethyl acetate *99:1), yielding 6 *Z1E).
1
*43.4); IR *®lm, cm21): 2200 *CN). H NMR *300 MHz,
CDCl3) d 6.82*d, Jˆ14.9 Hz, 1H); 7.11 *dd, Jˆ14.9,
11.3 Hz, 1H); 7.22 *d, Jˆ11.3 Hz, 1H); 7.27±7.39 *m,
6H); 7.40±7.50 *m, 2H); 7.55±7.62 *m, 2H); 13C NMR
*75 MHz, CDCl3) d 99.4, 116.4, 124.4, 127.5, 127.7,
129.0, 129.6, 129.7, 133.9, 135.3. Anal. calcd for
C17H13NSe: C, 65.81; H, 4.22. Found: C, 65.84; H, 4.12.
4.2.8. ꢀ1E,3E)-5-Phenyl-2-phenylselanyl-penta-2,4-diene-
nitrile ꢀ4g). Yield 0.031 g *10%). IR *KBr, cm21): 2202
1
*CN). H NMR *300 MHz, CDCl3) d 7.02*d, Jˆ14.5 Hz,
1H); 7.02*dd, Jˆ14.5, 11.0 Hz, 1H); 7.30 *d, Jˆ11.0 Hz,
1H); 7.34±7.45 *m, 6H); 7.50±7.57 *m, 2H); 7.58±7.65 *m,
2H); 13C NMR *100 MHz, CDCl3) d 101.3, 118.6, 124.7,
125.9, 127.7, 128.9, 129.0, 129.7, 129.9, 133.8, 135.6,
142.5, 149.0. Anal. calcd for C17H13NSe: C, 65.81; H,
4.22. Found: C, 66.04; H, 4.27.
*6Z): Yield 0.170 g *59%). MS m/z *rel. int.) 288 *M1,
57.4), 157 *34.6), 131 *100.0), 103 *74.4), 77 *87.5); IR
1
*®lm, cm21): 1690 *CO). H NMR *400 MHz, CDCl3) d
7.16±7.20 *m, 3H); 7.30±7.45 *m, 5H); 7.83±7.87 *m,
2H); 8.00 *s, 1H); 9.50 *s, 1H); 13C NMR *50 MHz,
CDCl3) d 127.1, 128.3, 129.1, 130.7, 130.9, 131.7, 132.1,
134.0, 152.5, 191.2. Anal. calcd for C15H12OSe: C, 62.73; H,
4.21. Found: C, 62.25; H, 4.31.
4.2.9. ꢀZ1E)-2-Phenyltellanyl-hex-2-enenitrile ꢀ5a).
Yield 0.280 g *93%). MS m/z *rel. int.) 299 *M1, 56.8),
205 *83.3), 142 *31.9), 129 *42.8), 77 *100.0); IR *®lm,
1
*6E) Yield 0.050 g *17%). IR *KBr, cm21): 1660 *CO). H
1
cm21): 2201 *CN). H NMR *300 MHz, CDCl3) d *Z1E)
NMR *200 MHz, CDCl3) d 7.20±7.45 *m, 9H), 7.60±7.70
*m, 2H); 9.78 *s, 1H); 13C NMR *50 MHz, CDCl3) d 126.6,
128.5, 129.0, 129.3, 129.5, 129.8, 134.7, 136.4, 138.4,
145.4, 188.8. Anal. calcd For C15H12OSe: C, 62.73; H,
4.21. Found: C, 62.72; H, 4.21.
0.90±1.00 *m, 3H); 1.42±1.58 *m, 2H); 2.22±3.33 *E) and
2.38±2.48 *Z) *2m, 2H); 6.88 *E) and 6.96 *Z) *2t,
Jˆ7.1 Hz, 1H); 7.24±7.42 *m, 3H); 7.78±7.88 *m, 2H);
13C NMR *50 MHz, CDCl3) d 13.2, 13.5, 21.1, 21.3, 37.1,
38.2, 79.2, 86.2, 112.1, 112.8, 117.8, 118.9, 128.8, 129.0,
129.5, 138.6, 139.3, 158.5, 164.1. Anal. calcd for
C12H13NTe: C, 48.23; H, 4.38. Found: C, 48.50; H, 4.27.
4.2.14. ꢀ2Z,4E)-2-Phenylseleno-5-phenyl-2,4-pentadien-
1-al 7 from ꢀZ)-4g. Yield 0.173 g *55%). MS m/z *rel.
int.) 314 *M1, 42.0), 157 *21.6), 128 *100.0), 77 *20.1);
1
4.2.10. ꢀZ1E)-2-Phenyltellanyl-hept-2-enenitrile ꢀ5b).
Yield 0.255 g *81%). MS m/z *rel. int.) 313 *M1, 35.8),
207 *59.0), 142 *49.7), 129 *27.7), 77 *100.0); IR *®lm,
IR *®lm, cm21): 1679 *CO). H NMR *400 MHz, CDCl3)
d 7.09 *d, Jˆ15.6 Hz, 1H); 7.14±7.22 *m, 3H); 7.28±7.35
*m, 3H); 7.38±7.43 *m, 4H); 7.47 *dd, Jˆ15.6, 10.8 Hz,
1H); 7.63 *d, Jˆ10.8 Hz, 1H); 9.44 *s,1H); 13C NMR
*50 MHz, CDCl3) d 125.8, 126.9, 127.7, 128.7, 129.1,
129.7, 129.8, 131.5, 132.9, 135.4, 144.5, 154.2, 190.5.
Anal. calcd for C17H14OSe: C, 65.18; H, 4.50. Found: C,
64.99; H, 4.65.
1
cm21): 2202 *CN). H NMR *300 MHz, CDCl3) d *Z1E)
0.87±0.98 *m, 3H); 1.28±1.55 *m, 4H); 2.26±2.35 *E) and
2.40±2.52 *Z) *2m, 2H); 6.89 *E) and 6.98 *Z) *2 t,Jˆ
7.4 Hz, 1H); 7.25±7.43 *m, 3H); 7.78±7.90 *m, 2H); 13C
NMR *50 MHz, CDCl3) d 13.5, 13.6, 21.9, 22.1, 29.8,
30.1, 35.0, 36.1, 79.0, 86.0, 112.1, 112.8, 117.9, 119.0,
128.9, 129.1, 129.6, 138.7, 139.5, 158.8, 164.5. Anal.
calcd for C13H15NTe: C, 49.91; H, 4.83. Found: C, 49.89;
H, 4.75.
4.2.15. Preparation of 8. A solution *1R, 2S)-*2)-ephe-
drine *0.165 g, 1 mmol) in EtOH *1.0 mL) was added drop-
wise to a solution of the 4d *0.208 g, 1 mmol) in EtOH
*1.0 mL) at rt. The reaction was stirred at this temperature
for 3 h. The solvent was removed in vacuo and the residue
incorporated into SiO2 and puri®ed by ¯ash column
chromatography, eluted with hexane/ethyl acetate *85:15),
to afford 8.21
4.2.11. ꢀZ1E)-4-Methyl-2-phenyltellanyl-pent-2-eneni-
trile ꢀ5c).21 Yield 0.235 g *78%). MS m/z *rel. int.) 299
*M1, 33.6), 207 *54.7), 77 *100.0); IR *®lm, cm21): 2202
*CN). 1H NMR *200 MHz, CDCl3) d 1.04 *E) and 1.06 *Z)
*2d, Jˆ6.6 Hz, 6H); 2.55±2.73 *E) and 2.74±2.96 *2m, 1H);
6.66 *E) and 6.80 *Z) *2d, Jˆ9.6 Hz, 1H); *Z1E) 7.23±7.40
*m, 3H); 7.77±7.87 *m, 2H); 13C NMR *50 MHz, CDCl3) d
21.1, 21.5, 35.1, 36.2, 76.9, 83.4, 112.1, 112.8, 117.8, 119.0,
128.9, 129.2, 129.7, 138.7, 139.6, 164.6, 170.4.
Yield 0.250 g *67%). MS m/z *rel. int.) 118 *M121,
±C10H11N2Se and OH, 19.2), 110 *17.2), 105 *60.3), 77
1
*100.0), 58 *63.4); IR *®lm, cm21): 2232 *CN). H NMR
*200 MHz, CDCl3) d 0.95 *d, Jˆ7.0 Hz, 3H); 2.33 and 2.34
*2s, 3H); 2.53 *s, broad, 1H); 2.75±3.10 *m, 3H); 3.63 *dd,
Jˆ9.0, 6.4 Hz, 0.5H); 3.73 *t, Jˆ7.4 Hz, 0.5H); 4.75±4.78
*m, 1H); 7.20±7.45 *m, 8H); 7.66±7.74 *m, 2H); 13C NMR
*50 MHz, CDCl3) d 9.8, 9.9, 26.3, 26.6, 38.9, 39.0, 56.9,
57.1, 64.6, 64.7, 74.4, 74.7, 119.7, 125.9, 126.0, 126.0,
126.1, 127.2, 128.1, 129.5, 136.2, 142.2, 142.4. Anal.
calcd for C19H22N2OSe: C, 61.12; H, 5.94. Found: C,
59.49; H, 5.72.
4.2.12. 2-Phenyltellanylacrylonitrile ꢀ5d).21 Yield 0.060 g
*23%). MS m/z *rel. int.) 259 *M112, 35.8), 207 *68.0), 129
*66.4), 77 *100.0), 51 *47.0); IR *®lm, cm21): 2206 *CN). 1H
NMR *200 MHz, CDCl3) d 6.30 *s, 1H); 6.95 *s, 1H); 7.20±
7.50 *m, 3H); 7.86±7.93 *m, 2H); 13C NMR *50 MHz,
CDCl3) d 90.5, 112.0, 118.7, 129.7, 130.1, 140.2, 142.6.
4.2.13. Synthesis of ꢀZ1E)-2-phenylseleno-3-phenyl-2-
propen-1-al 6 from 4f. A solution of diisobutylaluminum
4.2.16. Preparation of 9. The same procedure as above was

C. C. Silveira et al. / Tetrahedron 5732001) 5953±5959
5959
P. M.; Detty, M. R. J. Org. Chem. 1998, 63, 5403. Bella,
M.; D'Onofrio, F.; Margarita, R.; Parlanti, G.; Piancatelli,
G.; Mangoni, A. Tetrahedron Lett. 1997, 38, 7917.
followed using piperidine *0.085 g, 1 mmol). The reaction
was performed solvent-free and was stirred at rt for 5 min.
The compound 9 was obtained as a yellow oil.21
2. Aggarwal, V. K.; Anderson, E. S.; Elfyn Jones, D.; Obierey,
K. B.; Giles, R. J. Chem. Soc., Chem. Commun. 1998, 1985.
Boucher, J.-L.; Stella, L. Tetrahedron 1986, 42, 3871.
Boucher, J.-L.; Stella, L. Tetrahedron Lett. 1985, 26, 5041.
Stella, L.; Boucher, J.-L. Tetrahedron Lett. 1982, 23, 953.
Pochat, F. Tetrahedron Lett. 1983, 24, 5073. De Cock, Ch.;
Yield 0.240 g *82%). MS m/z *rel. int.) 209 *M121,
±C5H10N, 6.6), 182*7.1), 98 *100.0), 77 *35.5); IR *®lm,
1
cm21): 2232 *CN). H NMR *200 MHz, CDCl3) d 1.35±
1.48 *m, 2H); 1.50±1.65 *m, 4H); 2.30±2.52 *m, 4H);
2.77 *d, Jˆ7.4 Hz, 2H); 3.80 *t, Jˆ7.4 Hz, 1H); 7.25±7.40
*m, 3H); 7.68±7.74 *m, 2H); 13C NMR *50 MHz, CDCl3) d
23.9, 25.3, 25.7, 54.3, 60.1, 119.9, 126.3, 129.5, 136.2.
Anal. calcd for C14H18N2Se: C, 57.34; H, 6.19. Found: C,
56.79; H, 5.97.
Â
Piettre, S.; Lahousse, F.; Janousek, Z.; Merenyi, R.; Viehe,
H. G. Tetrahedron 1985, 41, 4183.
3. Brownbridge, P.; Durman, J.; Hunt, P. G.; Warren, S. J. Chem.
Soc., Perkin Trans. 1 1986, 1947. Durman, J.; Hunt, P. G.;
Warren, S. Tetrahedron Lett. 1983, 24, 2113.
4.2.17. Preparation of 2-phenylselanyl-bicyclo[2.2.1]-
hept-5-ene-2-carbonitrile ꢀ11). A solution of EtAlCl2
*1.4 mmol, 1.0 M solution in hexane) was added dropwise
to a solution of nitrile 4d *1.0 mmol) in dichloromethane
*3.0 mL) at 2788C under nitrogen. The reaction was stirred
at this temperature for 5 min, cyclopentadiene *0.2mL) was
added, and the mixture was stirred for 2.5 h. The mixture
was poured into water and the product was extracted with
ethyl acetate *3£25 mL). The organic layer was dried over
MgSO4 and the solvent removed in vacuo. The residue was
puri®ed by column chromatography over silica gel and
eluted with hexane/ethyl acetate *98:2), yielding 11.
4. Martin, C.; Mailliet, P.; Maddaluno, J. Org. Lett. 2000, 2, 923.
Silveira, C. C.; Nunes, M. R. S.; Wendling, E.; Braga, A. L.
J. Organomet. Chem. 2001, 623, 131.
5. Bella, M.; Margarita, R.; Orlando, C.; Orsini, M.; Parlanti, L.;
Piancatelli, G. Tetrahedron Lett. 2000, 41, 561. D'onofrio, F.;
Margarita, R.; Parlanti, L.; Piancatelli, G.; Sbraga, M. J. Chem.
Soc., Chem. Commun. 1998, 185. D'Onofrio, F.; Parlanti, L.;
Piancatelli, G. Synlett 1996, 63. Angoh, A. G.; Clive, D. L. J.
J. Chem. Soc., Chem. Commun. 1985, 941.
È
6. Dopp, D.; Sturm, T. Liebigs Ann./Recueil 1997, 541.
7. Han, D. I.; Oh, D. Y. Synth. Commun. 1988, 18, 2111. Pochat,
F. Tetrahedron Lett. 1978, 2683.
8. *a) Janousek, Z.; Piettre, S.; Gorissen-Hervens, F.; Viehe,
H. G. J. Organomet. Chem. 1983, 250, 197. *b) Piettre, S.;
Yield 0.200 g *73%). MS m/z *rel. int.) 275 *M111, 13.2),
209 *100.0), 182 *67.5), 157 *36.5), 91 *70.8), 77 *48.1); IR
Â
Janousek, Z.; Merenyi, R.; Viehe, H. G. Tetrahedron 1985, 41,
2527.
1
*KBr, cm21): 2229 *CN). H NMR *400 MHz, CDCl3) d
*endo) 1.41 *dd, Jˆ12.8, 2.1 Hz, 1H); 1.73±1.75 *m, 2H);
2.45 *dd, Jˆ12.8, 3.7 Hz, 1H); 3.07±3.13 *m, 1H); 3.15±
3.17 *m, 1H); 6.15 and 6.31 *2dd, Jˆ5.6, 3.0 Hz, 2H); *exo)
1.63±1.67 *m, 1H); 1.89 *dd, Jˆ12.7, 2.5 Hz, 1H); 2.04 *dd,
Jˆ12.7, 3.5 Hz, 1H); 2.04±2.07 *m, 1H); 3.00±3.02 *m,
9. Silveira, C. C.; Perin, G.; Braga, A. L.; Dabdoub, M. J.; Jacob,
R. G. Tetrahedron 1999, 55, 7421 and references therein.
10. Dawson, N. D.; Burger, A. J. Am. Chem. Soc. 1952, 74, 5312.
11. Dinizo, S. E.; Freerksen, R. W.; Edward Pabst, W.; Watt, D. S.
J. Org. Chem. 1976, 41, 2846.
1H); 3.04±3.07 *m, 1H); 6.12and 6.35 *d2d,
Jˆ5.6,
12. Silveira, C. C.; Perin, G.; Lang, E. S.; Braga, A. L., to be
published.
3.0 Hz, 2H); *endo1exo) 7.35±7.50 *m, 6H); 7.74±7.80
*m, 4H); 13C NMR *100 MHz, CDCl3) d *endo) 38.6,
40.4, 42.5, 47.8, 52.2, 124.0, 126.9, 129.3, 129.6, 133.5,
136.8, 138.0, *exo) 37.9, 41.6, 43.3, 46.7, 50.9, 123.4,
127.1, 129.4, 129.8, 133.5, 137.1, 139.9. Anal. calcd for
C14H13NSe: C, 61.32; H, 4.78. Found: C, 61.22; H, 4.80.
13. Yoshimatsu, M.; Oguri, K.; Ikeda, K.; Gotoh, S. J. Org. Chem.
1998, 63, 4475.
14. *a) Lerouge, P.; Paulmier, C. Bull. Soc. Chim. Fr. 1985, 1225.
*b) Uneyama, K.; Takano, K.; Torii, S. Tetrahedron Lett.
1982, 23, 1161. *c) Reich, H. J.; Shah, S. K.; Gold, P. M.;
Olson, R. E. J. Am. Chem. Soc. 1981, 103, 3112. *d) Back,
T. G.; Dyck, B. P. Tetrahedron Lett. 1992, 33, 4725.
15. *a) Back, T. G.; Dyck, B. P. Tetrahedron Lett. 1992, 4725.
*b) Uneyama, K.; Takano, K.; Torii, S. Bull. Chem. Soc. Jpn
1983, 56, 2867.
4.2.18. Preparation of 4-methyl-1-phenylselanyl-cyclo-
hex-3-ene-carbonitrile ꢀ10).21 The same procedure as
above was followed using isoprene *0.2mL). However,
the reaction was stirred at 2788C for 1 h and was allowed
to reach rt for 1 h and stirred for 2h at this temperature.
16. Hanessian, S.; Yang, H.; Schaum, R. J. Am. Chem. Soc. 1996,
118, 2507.
Yield 0.190 g *69%). MS m/z *rel. int.) 277 *M111, 18.0),
17. Hanessian, S.; Yang, H. Tetrahedron Lett. 1997, 38, 3155.
18. Torchiarolo, G. C.; D'Onofrio, F.; Margarita, R.; Parlanti, L.;
Piancatelli, G.; Bella, M. Tetrahedron 1998, 54, 15657.
19. Berlin, S.; Engman, L. Tetrahedron Lett. 2000, 41, 3701.
20. *a) Fringhelli, F.; Taticchi, A. Dienes in the Diels±Alder Reac-
tion, Wiley: New York, 1990. *b) Aggarwal, V. K.; Ali, A.;
Coogan, M. P. Tetrahedron 1999, 55, 293.
157 *18.7), 120 *79.0), 93 *100.0); IR *®lm, cm21): 2225
*CN). H NMR *400 MHz, CDCl3) d 1.68 *s, 3H); 1.89±
1
1.97 *m, 1H); 2.05±2.26 *m, 3H); 2.48 *AB, Jˆ17.3 Hz,
2H); 5.25±5.30 *m, 1H); 7.35±7.40 *m, 2H); 7.42±7.47
*m, 1H); 7.76±7.79 *m, 2H); 13C NMR *100 MHz, CDCl3)
d 23.4, 28.2, 32.4, 34.8, 36.2, 117.0, 122.3, 125.6, 129.4,
130.1, 134.4, 137.9. Anal. calcd For C14H15NSe: C, 60.87;
H, 5.47. Found: C, 61.63; H, 5.48.
21. Some of the prepared compounds were not stable to get
correct elemental analysis, although they were pure as indi-
1
cated by H and 13C NMR spectra *exception for 8 and 9,
always contaminated by a very small amount of 4d formed
by a retro-Michael reaction during silica gel column chroma-
tography puri®cation).
References
1. Zhou, F.; Rosen, J.; Zebrowski-Young, J. M.; Freihammer,