New preparation of (Z)-1-phenyl-3-cyano-2-propen-1-ones

Article abstract of DOI:10.1080/00397911.2010.497598

Reaction of γ-phenyl-β,γ-unsaturated hydroxamates with bis(collidine)-bromine(I) hexafluorophosphate led to the formation of cyclic bromo imidates. Reaction of these with triethylamine led to the formation of 3-cyano-2-propen-1-ones with good yields by a

Full text of DOI:10.1080/00397911.2010.497598

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New Preparation of (Z)-1-Phenyl-3-
cyano-2-propen-1-ones
Houssam Trabulsi a & Gérard Rousseau a
a Laboratoire de Synthèse Organique et Méthodologie, ICMMO,
Universite Paris-Sud, Orsay, France
Available online: 20 May 2011
To cite this article: Houssam Trabulsi & Gérard Rousseau (2011): New Preparation of (Z)-1-Phenyl-3-
cyano-2-propen-1-ones, Synthetic Communications: An International Journal for Rapid Communication
of Synthetic Organic Chemistry, 41:14, 2123-2134
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Synthetic Communications1, 41: 2123–2134, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2010.497598
NEW PREPARATION OF (Z)-1-PHENYL-3-CYANO-
2-PROPEN-1-ONES
´
Houssam Trabulsi and Gerard Rousseau
Laboratoire de Synthese Organique et Methodologie, ICMMO, Universite
`
´
Paris-Sud, Orsay, France
GRAPHICAL ABSTRACT
Abstract Reaction of c-phenyl-b,c-unsaturated hydroxamates with bis(collidine)-
bromine(I) hexafluorophosphate led to the formation of cyclic bromo imidates. Reaction
of these with triethylamine led to the formation of 3-cyano-2-propen-1-ones with good yields
by a fragmentation reaction.
Keywords Aryl compound; bromonium; 5-endo cyclization; enone; nitrile
INTRODUCTION
We are engaged in a program concerning the study of the reactivity of bis
(collidine)bromine(I) hexafluorophosphate as an electrophile.[1] Recently, we exam-
ined the reaction of b,c-unsaturated hydroxamates with this bromo reagent. The
reactivity of unsaturated hydroxamates with electrophiles has been only briefly
reported in the literature. Formation of lactams was observed using bromine or
N-bromosuccinimide.[2] On the other hand, a mixture of c-butyrolactams and
immonium salts was generally obtained with selenium reagents.[3]
RESULTS
The hydroxamate 3 was prepared in two steps in good yield from the commer-
cially available trans-styrilacetic acid 1, by reaction of the acid chloride with hydro-
xylamine followed by acetylation. Reaction of this compound with bis(collidine)
Received May 6, 2010.
Address correspondence to Gerard Rousseau, Laboratoire de synthese Organique et Methodologie,
´
ICMMO, Universite Paris-Sud, F-91405 Orsay, France. E-mail: gerard.rousseau@u-psud.fr
`
2123

2124
H. TRABULSI AND G. ROUSSEAU
Scheme 1. Preparation of 4-oxo-4-phenylbut-2-enenitrile 6.
bromine(I) hexafluorophosphate in dichloromethane at room temperature led to the
formation of a mixture of the cyclic bromo imine 4, the corresponding HBr
elimination product 5, and the unsaturated nitrile 6 (Scheme 1). Large degradation
of these products was observed during their purification over silica gel. To avoid the
yield loss during their purification, the crude reaction product was reacted with 1
equivalent of triethylamine: (Z)-4-oxo-4-phenylbut-2-enenitrile 6 was obtained in
good yield as a unique product. This compound was characterized from its NMR
and infrared (IR) spectra and by comparison of its spectra with those reported in
the literature.[4,5] The formation of compound 6 can probably be explained by a
Beckmann fragmentation,[6] initiated by abstraction of the hydrogen in a of the
oxygen atom as indicated in Scheme 1.
Then, we decided to examine the case of 2-substituted styrilacetic acids. These
different compounds have been prepared as reported in Scheme 2. 2-Subtituted deri-
vatives 7a–e were obtained by alkylation of styryl acid, and (E)-2,4-diphenylbut-3-
enoic acid 9 has been obtained by carbonation of (E)-1,3-diphenylprop-1-ene. The
hydroxamates were then obtained by reaction of the corresponding acid chlorides
with hydroxylamine, followed by acetylation. In the case of the formation of the
hydroxamate 11e, a side reaction was observed, leading to the minor formation of
the succinimide 12. Reaction of these compounds with bis(collidine)bromine(I) hex-
afluorophosphate in dichloromethane at room temperature led to the formation of
the few stable cyclic bromo imidates. In all cases, only one diastereoisomer was
formed, and its stereochemistry was deduced from our previous results concerning
the cyclization of the corresponding acids.[7] After reaction with triethylamine, these
cyclic bromo imidates led to the formation of 3-cyano-2-propen-1-ones. The struc-
tures of these compounds were easily established from their spectra data. Only
one isomer was formed. In the case of compound 14f (R1 ¼ phenyl), the stereochem-
istry was clearly established by comparison of its spectra with those reported in the
literature. The stereochemistries observed in the formation of 6 and 14f led us to

(Z)-1-PHENYL-3-CYANO-2-PROPEN-1-ONES
2125
Scheme 2. Preparation of 1-phenyl-3-cyano-2-propen-1-ones 14a–f.
Scheme 3. Substituted b-cyano enones.
propose also a Z stereochemistry for compounds 14a–e. This family of compounds
is already reported in the literature (see the experimental section). Formation of
b-cyano disubstituted[4,8] (type A, Scheme 3) and trisubstituted[9] enones (type B)
has been reported. Because enones have an important place in organic synthesis,[10]
we think this new formation of these highly functionalized compounds can be
interesting in synthesis.
EXPERIMENTAL
All reactions were carried out under argon. Purification of products was
carried out by normal-phase flash chromatography.

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H. TRABULSI AND G. ROUSSEAU
(E)-N-Hydroxy-4-phenylbut-3-enamide 2
Oxalyl chloride (0.2 mL, 2.275 mmol, 1.75 eq.) was added dropwise to a
CH2Cl2 solution (5 mL) of commercial (E)-4-phenylbut-3-enoic acid 1 (0.210 g,
1.3 mmol) cooled at 0 ꢀC. The solution was stirred one night at rt and then concen-
trated under vacuum. An aqueous solution of hydroxyamine (4.5 mL of a 2.5 M sol-
ution prepared from an equimolar mixture of NþH3OH Clꢁ and NaOH, 7 eq.) was
added to the acid chloride. There was formation of a white solid, which was isolated
by filtration. The filtrate was extracted twice with CH2Cl2(10 mL). The organic
phases were dried (MgSO4) and concentrated under vacuum. The residue was added
1
to the previous solid. Yield: 0.221 g, 96%. Mp 135–137 ꢀC. H NMR (MeOH-d4,
250 MHz) d: 7.33–7.11 (m, 5H), 6.47 (d, J ¼ 16.0 Hz, 1H), 6.23 (dt, J ¼ 7.0 and
16.0 Hz, 1H), 2.97 (d, J ¼ 7.0 Hz, 2H). 13C NMR (MeOH-d4, 62.9 MHz) d: 169.6,
136.9, 133.4, 128.4, 127.2, 126.0, 122.0, 36.6. IR (MeOH-d4, cmꢁ1): 3344, 3031,
1650. HR MS: calculated for C10H11NNaO2 (M þ Naþ): 200.0687. Found: 200.0690.
(3E)-N-(Acetoxy)-4-phenylbut-3-enamide 3
Pyridine (30 mL, 1.06 eq.) was added to a tetrahydrofuran (THF) solution
(10 mL) of hydroxamic acid 2 (69 mg, 0.39 mmol) cooled at 0 ꢀC in 10 min. The sol-
ution was stirred 20 min at rt, and acetyl chloride (40 mL, 1.06 eq.) was added drop-
wise. After 2 h at rt, ether (5 mL) was added, and the homogenous organic solution
was washed successively with water (5 mL), aqueous 0.5 M HCl solution (5 mL), and
saturated NaCl solution (5 mL). The organic phase was dried (MgSO4) and concen-
trated under vacuum to give a white solid, which was used without further purifi-
1
cation for the next step. Yield: 66 mg, 77%. Mp 131–133 ꢀC. H NMR (CDCl3,
360 MHz) d: 9.0 (br. s, 1H), 7.38–7.25 (m, 5H), 6.59 (d, J ¼ 15.8 Hz, 1H), 6.29 (dt,
J ¼ 15.8 and 7.4 Hz, 1H), 3.25 (d, J ¼ 7.3 Hz, 2H), 2.22 (s, 3H). 13C NMR (CDCl3,
62.9 MHz) d: 169.3, 168.7, 136.3, 135.0, 128.6, 127.9, 126.3, 120.4, 37.5, 18.2. IR
(CH2Cl2, cmꢁ1): 3148, 2964, 1792, 1662. HR MS: calculated for C12H13NNaO3
(M þ Naþ): 242.0793. Found: 242.0803.
Reaction of Hydroxamate 3 with Bis(collidine)bromine(I)
Hexafluorophosphate
Bis(collidine)bromine(I) hexafluorophosphate[11] (307 mg, 0.66 mmol) was
added to a dichloromethane solution (10 mL) of hydroxamate 3 (131 mg, 0.6 mmol).
1
After 2 h at rt, the solvent was removed under vacuum. The H NMR of the crude
reaction mixture showed the presence of three products: the bromo imidate 4 (47%),
the unsaturated imidate 5 (30%), and the nitrile 6 (23%). Purification of this mixture
by liquid chromatography over silica gel led to intensive degradations. Only small
amounts of these compounds were isolated.
(2Z)-4-Bromo-5-phenyldihydrofuran-2(3H)-one O-Acetyloxime 4
Oil. 1H NMR (CDCl3, 250 MHz) d: 7.37–7.20 (m, 5H), 5.66 (d, J ¼ 4.8 Hz, 1H),
4.29 (ddd, J ¼ 4.8, 5.8 and 7.0 Hz, 1H), 3.40 (dd, J ¼ 17.5 and 7.0 Hz, 1H), 3.12 (dd,

(Z)-1-PHENYL-3-CYANO-2-PROPEN-1-ONES
2127
J ¼ 17.5 and 5.8 Hz, 1H), 2.17 (s, 3H). 13C NMR (CDCl3, 62.9 MHz) d: 168.0, 162.2,
135.1, 129.5, 129.1, 125.4, 92.3, 46.1, 37.0, 19.3. IR (film, cmꢁ1): 2902, 1767, 1679.
HR MS: calculated for C12H12BrNNaO3 (M þ Naþ): 319.9898. Found: 319.9899.
(2Z)-5-Phenyl-2(5H)-furanone O-Acetyloxime 5
1H NMR (CDCl3, 250 MHz) d: 7.37–7.20 (m, 5H), 7.04 (d, J ¼ 5.7 Hz, 1H),
6.34 (d, J ¼ 5.7 Hz, 1H), 6.29 (br. s, 1H), 2.15 (s, 3H).
(Z)-4-Oxo-4-phenylbut-2-enenitrile 6
After reaction of hydroxamate 3 with bis(collidine)bromine(I) hexafluoropho-
sphate, triethylamine (2 eq.) was added to the reaction mixture. After stirring for 2 h
at rt, the mixture was concentrated under vacuum, and the residue was purified by
liquid chromatography over silica gel to give compound 6[4,5] as a white solid (mp
77 ꢀC, 87%). 1H NMR (CDCl3, 360 MHz) d: 7.97 (d, J ¼ 7.2 Hz, 2H), 7.64 (d,
J ¼ 11.5 Hz, 1H), 7.63 (m, 1H), 7.54 (dd, J ¼ 7.2 and 7.2 Hz, 2H), 6.00 (d, J ¼ 11.5,
1H). 13C NMR (CDCl3, 62.9 MHz) d: 186.6, 141.7, 135.4, 134.2, 128.9, 128.6,
115.4, 108.8. IR (CH2Cl2, cmꢁ1): 3084, 3054, 2965, 2928, 1671, 1603, 1579, 908,
732. HR MS: calculated for C10H7NNaO (M þ Naþ): 180.0425. Found: 180.0427.
Preparation of Acids 7a–e
These compounds have been prepared by alkylation of the anion formed by
reaction of (E)-4-phenylbut-3-enoic acid 1 with butyl lithium.[12]
(E)-2-Methyl-4-phenylbut-3-enoic acid 7a[13]. Yield: 61%. 1H NMR (CDCl3,
250 MHz) d (ppm): 11.00 (bs, 1H), 7.27–7.42 (m, 5H), 6.63 (d, J ¼ 16.1 Hz, 1H), 6.41
(dd, J ¼ 15.9 and 7.75 Hz, 1H), 3.45 (dd, J ¼ 14.5 and 7.4 Hz, 1H), 1.52 (d,
J ¼ 6.9 Hz, 3H). 13C NMR (CDCl3, 63 Hz) d (ppm): 181.2, 136.6, 131.6, 128.4
(2C), 127.8, 127.5, 126.3 (2C), 42.9, 17.1. IR (CH2Cl2) t (cmꢁ1): 3300, 3027, 2979,
2936, 1706, 1415, 1213, 965, 693. LR MS: 194.0 ðM þ NHþ4 ; 100Þ.
(E)-2-Ethyl-4-phenylbut-3-enoic acid 7b[12]. Yield: 81%. 1H NMR (CDCl3,
250 MHz) d (ppm): 11.71 (bs, 1H), 7.55–7.17 (m, 5H), 6.59 (d, J ¼ 15.9 Hz, 1H), 6.27
(dd, J ¼ 15.9 and 8.9 Hz, 1H), 3.18 (dd, J ¼ 16.0 and 7.3 Hz, 1H), 1.98 (septuplet,
7.3 Hz, 1H), 1.76 (septuplet, 7.4 Hz, 1H), 1.06 (t, J ¼ 7.4 Hz, 3H). 13C NMR (CDCl3,
63 Hz) d (ppm): 180.0, 136.4, 132.5, 128.2 (2C), 127.3, 126.5, 126.1 (2C), 50.9, 25.4,
11.4. IR (CH2Cl2) t (cmꢁ1): 3200, 2934, 1702, 1268, 966, 745, 692. LR MS: 208.0
ðM þ NHþ4 ; 100Þ.
(E)-2-Benzyl-4-phenylbut-3-enoic acid 7c[14]. Yield: 81%. 1H NMR (CDCl3,
250 MHz) d (ppm): 11.35 (bs, 1H), 7.64–7.18 (m, 10H), 6.52 (d, J ¼ 15.9 Hz, 1H),
6.31 (dd, J ¼ 15.9 and 8.7 Hz, 1H), 3.59 (dd, J ¼ 15.7 and 7.6 Hz, 1H), 3.30 (dd,
J ¼ 13.7 and 7.5 Hz, 1H), 3.05 (dd, J ¼ 13.7 and 7.3 Hz, 1H). 13C NMR (CDCl3,
75.5 Hz) d (ppm): 179.9, 138.1, 136.4, 133.2, 129 (2C), 128.4 (2C), 127.7 (2C),
126.5, 126.3 (2C), 125.9 (2C), 51.1, 38.5. IR (CH2Cl2) t (cmꢁ1): 3200, 2957, 1692,
1455, 1413, 1290, 965, 754, 696. LR MS: 270.0 ðM þ NHþ4 ; 100Þ.

2128
H. TRABULSI AND G. ROUSSEAU
(E)-2-Styrylhex-5-enoic acid 7d. Yield: 81%. 1H NMR (CDCl3, 250 MHz) d
(ppm): 12.09 (bs, 1H), 7.58–7.21 (m, 5H), 6.61 (d, J ¼ 15.9 Hz, 1H), 6.27 (dd,
J ¼ 15.8, 9 Hz, 1H), 5.89 (m, 1H), 5.18 (t, J ¼ 12.4 Hz, 2H), 3.32 (dd, J ¼ 15.5 and
7.8 Hz, 1H), 2.35–2.16 (m, 2H), 2.16–1.85 (m, 2H). 13C NMR (CDCl3, 75.5 Hz) d
(ppm): 180.2, 137.2, 136.4, 132.8, 128.3 (2C), 127.5, 126.4, 126.2 (2C), 115.4, 48.7,
31.2, 30.9. IR (CH2Cl2) t (cmꢁ1): 3200, 2977, 1706, 1641, 1450, 1416, 1287, 966,
914, 746, 693. LR MS: 234.0 ðM þ NHþ4 ; 100Þ.
(E)-2-((Methoxycarbonyl)methyl)-4-phenylbut-3-enoic acid 7e. Yield:
83%. 1H NMR (CDCl3, 250 MHz) d (ppm): 10.9 (bs, 1H), 7.50–7.19 (m, 5H),
6.63 (d, J ¼ 15.9 Hz, 1H), 6.24 (dd, J ¼ 15.9 and 8.4 Hz, 1H), 3.84–3.64 (m, 4H),
2.99 (dd, J ¼ 16.7 and 8.5 Hz, 1H), 2.71 (dd, J ¼ 16.7 and 5.9 Hz, 1H). 13C
NMR (CDCl3, 62.9 Hz) d (ppm): 178.4, 171.6, 136.2, 133.7, 128.5 (2C), 127.9,
126.4 (2C), 124.5, 51.9, 44.7, 35.9. IR (CH2Cl2) t (cmꢁ1): 3200, 3025, 2957,
2936, 1732, 1696, 1423, 1298, 1164, 968, 743, 693. LR MS: 235.0 (M þ Hþ, 20),
252.0 ðM þ NHþ4 ; 100Þ.
(E)-2,4-Diphenylbut-3-enoic Acid 9
This acid has been prepared, as previously reported,[15] by carbonation of the
anion formed by reaction of 1,3-diphenyl-1-propene 8[16] with n-butyl lithium using
carbon dioxide (70%).
Preparation of N-Hydroxyamides 10a–f
These compounds were obtained by the procedure reported for the preparation
of compound 2.
(E)-N-Hydroxy-2-methyl-4-phenylbut-3-enamide 10a. Oil. Yield: 93%.
1H NMR (CDCl3, 250 MHz) d (ppm): 8.41–8.15 (m, 2H), 7.52–7.09 (m, 5H),
6.57 (d, J ¼ 15.9 Hz, 1H), 6.22 (dd, J ¼ 15.8 and 8.0 Hz, 1H), 3.34–3.07 (m, 1H),
1.44 (d, J ¼ 7.0 Hz, 3H). 13C NMR (CDCl3, 62.9 Hz) d (ppm): 171.2, 136.3,
132.6, 128.4 (2C), 127.7, 127.5, 126.3 (2C), 43.9, 17.2. IR (CH2Cl2) t (cmꢁ1):
3179, 3020, 2902, 1634, 1536, 1353, 909, 734, 699. LR MS: 192.1 (M þ Hþ, 40),
209.1 ðM þ NHþ4 ; 13Þ.
(E)-2-Ethyl-N-hydroxy-4-phenylbut-3-enamide 10b. White solid, mp
1
107 ꢀC. Yield: 99%. H NMR (CDCl3, 250 MHz) d (ppm): 8.30 (m, 2H), 7.53–7.16
(m, 5H), 6.52 (d, J ¼ 15.8 Hz, 1H), 6.16 (dd, J ¼ 15.8 and 8.7 Hz, 1H), 2.80 (m,
1H), 1.60 (m, 2H), 0.90 (t, J ¼ 7.4 Hz, 3H). 13C NMR (CDCl3–, 62.9 Hz) d (ppm):
171.8, 136.3, 133.6, 128.6 (2C), 127.9, 126.3 (3C), 49.5, 25.3, 11.6. IR (CH2Cl2) t
(cmꢁ1): 3669, 3024, 2928, 1623, 1496, 1096, 983, 737, 691. LR MS: 206.0 (M þ Hþ,
100), 223.0 ðM þ NHþ4 ; 32Þ.
(E)-2-Benzyl-N-hydroxy-4-phenylbut-3-enamide 10c. Yellow solid, mp
125.5 ꢀC. Yield: 81%. 1H NMR (CDCl3, 300 MHz) d (ppm): 11.35 (s, 1H),
7.64–7.18 (m, 10H), 6.52 (d, J ¼ 15.9 Hz, 1H), 6.31 (dd, J ¼ 15.9 and 8.7 Hz, 1H),
3.59 (dd, J ¼ 15.9 and 7.6 Hz, 1H), 3.30 (dd, J ¼ 13.7 and 7.6 Hz, 1H), 3.05 (dd,
J ¼ 13.7 and 7.3 Hz, 1H). 13C NMR (CDCl3, 75.5 Hz) d (ppm): 179.9, 138.1,

(Z)-1-PHENYL-3-CYANO-2-PROPEN-1-ONES
2129
136.4, 133.2, 129 (2C), 128.4 (2C), 127.7 (2C), 126.5, 126.3 (2C), 125.9 (2C), 51.1,
38.5. IR (CH2Cl2) t (cmꢁ1): 2957, 1692, 1455, 1413, 1290, 965, 754, 696. LR MS:
270.0 ðM þ NHþ4 ; 100Þ.
(E)-N-Hydroxy-2-styrylhex-5-enamide 10d. White solid, mp 48–49 ꢀC.
1
Yield: 93%. H NMR (CDCl3, 360 MHz) d (ppm): 9.00 (bs, 2H), 7.29 (m, 5H),
6.47 (d, J ¼ 15.6 Hz, 1H), 6.13 (dd, J ¼ 15, 8 Hz, 1H), 5.74 (m; 1H), 5.01 (dd,
J ¼ 16.7 and 8.3 Hz, 2H), 2.96 (bs, 1H), 2.15–1.86 (m, 3H), 1.70 (s, 1H). 13C NMR
(CDCl3, 75.5 Hz) d (ppm): 171.9, 137.3, 136.3, 133.5, 128.6 (2C), 127.8, 126.4,
126.3 (2C), 115.5, 46.8, 30.9 (2C). IR (CH2Cl2) t (cmꢁ1): 3697, 3182, 2922, 1629,
1525, 1265, 965, 749, 693. LR MS: 232.0 (M þ Hþ, 100), 249.1 ðM þ NH4þ; 13Þ.
(E)-Methyl 3-(Hydroxycarbamoyl)-5-phenylpent-4-enoate 10e. Oil. Yield:
1
55%. H NMR (CDCl3, 250 MHz) d (ppm): 9.60 (bs, 2H), 7.55–7.16 (m, 5H), 6.50
(bs, 1H), 6.10 (bs, 1H), 3.50 (m, 3H), 3.00–2.50 (m, 3H). 13C NMR (CDCl3,
62.9 Hz) d (ppm): 173.8, 172.4, 136, 135.8, 128.5 (2C), 127.9, 126.6 (2C), 124.9,
52.0, 43.2, 35.8. IR (CH2Cl2) t (cmꢁ1): 3182, 3024, 2921, 1656, 1545, 1369, 908,
765, 657. LR MS: 250.1 (M þ Hþ, 55), 267.1 ðM þ NH4þ; 13Þ.
(3E)-N-Hydroxy-2,4-diphenylbut-3-enamide 10f. White solid. Yield: 100%.
1H NMR (MeOH-d4, 360 MHz) d: 7.40–7.20 (m, 10H), 6.70–6.20 (m, 2H), 4.51
(d, J ¼ 6.8 Hz, 1H). 13C NMR (MeOH-d4, 62.9 MHz) d: 169.1, 137.5, 136.2, 133.3,
130.0, 128.8, 128.6, 127.5, 127.2, 126.4, 122.8, 48.5. HR MS: calculated for
C16H16NO2 (M þ Hþ): 254.1181. Found: 254.1185.
Preparation of N-Acetoxyamides 11a–f
These compounds were obtained by the procedure reported for the preparation
of compound 3.
(3E)-N-(Acetoxy)-2-methyl-4-phenyl-3-butenamide 11a. Oil. Yield: 90%.
1H NMR (CDCl3, 250 MHz) d (ppm): 8.99 (s, 1H), 7.49–7.22 (m, 5H), 6.62 (d,
J ¼ 15.84 Hz, 1H), 6.28 (dd, J ¼ 15.9 and 8.3 Hz, 1H), 3.45–3.19 (m, 1H), 2.25 (s,
3H), 1.45 (d, J ¼ 7.0 Hz, 3H). 13C NMR (CDCl3, 62.9 Hz) d (ppm): 168.7 (2C),
136.2, 132.7, 128.6 (2C), 127.9, 127.6, 126.3 (2C), 42.1, 18.2, 17.2. IR (CH2Cl2) t
(cmꢁ1): 3683,þ3152, 2978, 1794, 1651, 1656, 1530, 1370, 1176, 976, 852. LR MS:
234.0 (M þ H , 91), 251.1 ðM þ NHþ4 ; 54Þ.
(3E)-N-(Acetoxy)-2-ethyl-4-phenyl-3-butenamide 11b. White solid, mp
126 ꢀC. Yield: 87%. 1H NMR (CDCl3, 250 MHz) d (ppm): 9.16 (s, 1H),
7.51–7.12 (m, 5H), 6.58 (d, J ¼ 15.9 Hz, 1H), 6.23 (dd, J ¼ 15.9 and 8.8 Hz,
1H), 3.18 (dd, J ¼ 16.0 and 7.3 Hz, 1H), 2.24 (s, 3H), 1.99 (septuplet, J ¼ 7.1 Hz,
Hz, 1H), 1.72 (septuplet, J ¼ 7.4 Hz, 1H), 1(t, J ¼ 7.4 Hz, 3H). 13C NMR (CDCl3,
62.9 Hz) d (ppm): 168.7 (2C), 136.3, 133.5, 128.5 (2C), 127.8, 126.5, 126.3 (2C),
49.7, 25.3, 18.2, 11.5. IR (CH2Cl2) t (cmꢁ1): 3685, 3159, 2932, 1792, 1651,
1526, 1449, 1189, 972, 734. LR MS: 248 (M þ Hþ, 51), 265.1 ðM þ NH4þ; 89Þ.
(3E)-N-(Acetoxy)-2-benzyl-4-phenyl-3-butenamide 11c. White solid, mp
1
128 ꢀC. Yield: 90%. H NMR (CDCl3, 250 MHz) d (ppm): 9.00 (s, 1H), 7.48–7.11
(m, 10H), 6.50 (d, J ¼ 15.9 Hz, 1H), 6.27 (dd, J ¼ 15.9 and 8.3 Hz, 1H), 3.57–3.18

2130
H. TRABULSI AND G. ROUSSEAU
(m, 2H), 3.16–2.84 (m, 1H), 2.20 (s, 3H). 13C NMR (CDCl3, 90.5 Hz) d (ppm): 170.7,
168.4, 138.2, 136.2, 133.7, 129.1 (2C), 128.5 (2C), 127.8 (2C), 126.5, 126.3 (2C), 125.9
(2C), 50.0, 38.3, 18.2. IR (CH2Cl2) t (cmꢁ1): 3682, 3155, 2978, 2885, 1794, 1665,
1522, 1495, 1179, 1042, 970, 908, 848, 734, 706. LR MS: 310.0 (Mþ Hþ, 100), 327
ðM þ NHþ4 ; 17Þ.
(E)-N-Acetoxy-2-styrylhex-5-enamide 11d. Oil. Yield: 86%. 1H NMR
(CDCl3, 250 MHz) d (ppm): 9.51 (s, 1H), 7.57–7.11 (m, 5H), 6.57 (d, J ¼ 15.9 Hz,
Hz, 1H), 6.23 (dd, J ¼ 15.9 and 8.9 Hz, 1H), 5.82 (m, 1H), 5.08 (dd, J ¼ 20.6 and
5.3 Hz, 2H), 3.16 (dd, J ¼ 15.0 and 7.5 Hz, 1H), 2.35–1.96 (m, 6H), 1.80 (m, 1H.
13C NMR (CDCl3, 75.5 Hz) d (ppm): 171.5, 168.6, 137.5, 136.4, 133.5, 128.63
(2C), 127.9, 126.6, 126.4 (2C), 115.6, 47.1, 31.1, 30.9, 18.2. IR (CH2Cl2) t
(cmꢁ1): 3081, 3026, 2928, 2852, 1797, 1669, 1496, 1449, 1368, 1177, 1028, 968,
852, 745, 693. LR MS: 274.1 (M þ Hþ, 57), 291.1 ðM þ NH4þ; 13Þ.
Preparation of Hydroxamate 11e
In the conditions used for the preparation of compound 2, a mixture of two
products separable by liquid chromatography was obtained: the hydroxamate 11e
and the succinimide 12.
(E)-Methyl 3-(Acetoxycarbamoyl)-5-phenylpent-4-enoate 11e
Oil. Yield: 51%. 1H NMR (CDCl3, 360 MHz) d (ppm): 9.51 (bs, 1H), 7.55–7.21
(m, 5H), 6.66 (d, J ¼ 15.9 Hz, 1H), 6.26 (dd, J ¼ 15.9 and 8.8 Hz, 1H), 3.72(bs, 4H),
3.04 (dd, J ¼ 16.9 and 8.3 Hz, 1H), 2.69 (dd, J ¼ 16.9 and 5.7 Hz, 1H), 2.30–2.11 (bs,
3H). 13C NMR (CDCl3, 62.9 Hz) d (ppm): 172.0 (2C), 168.4, 136, 134.2, 128.5 (2C),
128, 126.4 (2C), 124.8, 51.9, 43.5, 36.1, 18.1. IR (CH2Cl2) t (cmꢁ1): 3790, 3232, 2789,
1794, 1694, 1665, 1660, 1420, 1375, 1150, 986, 865. LR MS: 292.1 (M þ Hþ, 85),
310.2 ðM þ NHþ4 ; 100Þ.
1-Acetoxy-3-(E)-2-styryl-2,5-pyrrolidinedione 12
1
Oil: 23%. H NMR (CDCl3, 360 MHz) d (ppm): 7.51–7.22 (m, 5H), 6.66 (d,
J ¼ 15.9 Hz, 1H), 6.19 (dd, J ¼ 15.9 and 7.4 Hz, 1H), 3.90–3.67 (bs, 1H), 3.14
(dd, J ¼ 18.1 and 9.1 Hz, 1H), 2.79 (dd, J ¼ 18.1 and 4.7 Hz, 1H), 2.34 (s, 3H).
13C NMR (CDCl3, 62.9 Hz) d (ppm): 169.8, 168.1, 165.4, 135.5, 134.7, 128.8 (2C),
128.5, 126.4 (2C), 122.4, 40.6, 32.3, 17.4. LR MS: 260.0 (M þ Hþ, 5), 277.0
ðM þ NHþ4 ; 100Þ.
(3E)-N-(Acetoxy)-2,4-phenylbut-3-enamide 11f
1
White solid, mp 117–118 ꢀC. Yield: 85%. H NMR (CDCl3, 250 MHz) d: 8.93
(br.s, 1H), 7.50–7.20 (m, 10H), 6.70–6.40 (m, 2H), 4.47 (d, J ¼ 6.8 Hz, 1H), 2.23
(s, 3H). 13C NMR (CDCl3, 62.9 MHz) d: 168.8, 168.7, 136.2, 135.2, 134.8, 130.1,
128.9, 128.7, 127.9, 127.4, 126.8, 120.5, 47.4, 18.4. HR MS: calculated for
C18H18NO3 (M þ Hþ): 296.1287. Found: 296.1287.

(Z)-1-PHENYL-3-CYANO-2-PROPEN-1-ONES
2131
Reaction of Hydroxamates 11a–f with Bis(collidine)bromine(I)
Hexafluorophosphate
Bis(collidine)bromine(I) hexafluorophosphate[11] (307 mg, 0.66 mmol) was
added to a dichloromethane solution (10 mL) of hydroxamate (0.6 mmol). After
2 h at rt, the solvent was removed under vacuum. The residue was purified by liquid
chromatography over silica gel (except for 13e–f).
(2Z,3Rꢂ,4Sꢂ,5Rꢂ)-4-Bromo-3-methyl-5-phenyl-dihydro-
2(3H)-furanone O-Acetyloxime 13a
1
Oil: 60%. H NMR (CDCl3, 360 MHz) d (ppm): 7.53–7.37 (m, 5H), 5.42 (d,
J ¼ 9.21 Hz, 1H), 3.84 (dd, J ¼ 10.6 and 9.3 Hz, 1H), 3.34 (m, 1H), 2.17 (s, 3H),
1.51 (d, J ¼ 6.75 Hz, 3H). 13C NMR (CDCl3, 62.9 MHz) d: 167.9, 164.3, 134.5,
129.6, 128.8, 126.7, 126.5 (2C), 89.1, 53.4, 45, 19.3, 13.3. LR MS: 312.0 (M þ Hþ, 100).
(2Z,3Rꢂ,4Sꢂ,5Rꢂ)-4-Bromo-3-ethyl-5-phenyl-dihydro-2(3H)-furanone
O-Acetyloxime 13b
Oil. 1H NMR (CDCl3, 360 MHz) d (ppm): 7.60–7.25 (m, 5H), 5.44 (d,
J ¼ 8.60 Hz, 1H), 4.00 (dd, J ¼ 9.8 and 8.7 Hz, 1H), 3.34 (td, J ¼ 9.8 and 5.8 Hz,
1H), 2.17 (s, 3H), 2.12–1.78 (m, 2H), 1.14 (t, J ¼ 7.5 Hz, 3H). 13C NMR (CDCl3,
62.9 MHz) d: 169.9, 166.6, 138.3, 129 (2C), 128.8, 126.3 (2C), 89.4, 55.3, 50.4,
21.2, 19.3, 11.6. LR MS: 325.9 (M þ Hþ, 100).
(2Z,3Rꢂ,4Sꢂ,5Rꢂ)-4-Bromo-3-benzyl-5-phenyl-dihydro-2(3H)-furanone
O-acetyloxime 13c
Oil: 57%. 1H NMR (CDCl3, 250 MHz) d: 7.50–7 (m, 10H), 6.69 (d, J ¼ 7.6 Hz,
1H), 4.62 (t, J ¼ 10.8 Hz, 1H), 3.6–3.4 (m, 1H), 3.34–3.1 (m, 2H), 2.26 (s, 3H). 13C
NMR (CDCl3, 62.9 MHz) d: 168.4, 164.2, 137, 133, 129.6 (4C), 129.4 (4C), 126.7,
126.2, 89.7, 55.7, 48.0, 34.2, 18.3. LR MS: 388 (M þ Hþ, 20), 405 ðM þ NH4þ; 100Þ.
(2Z,3Rꢂ,4Sꢂ,5Rꢂ)-4-Bromo-3-(3-buten-1-yl)-5-phenyl-dihydro-
2(3H)-furanone O-Acetyloxime 13d
Oil: 55%. 1H NMR (CDCl3, 360 MHz) d (ppm): 7.64–7.18 (m, 5H), 5.93–5.77 (m,
1H), 5.45 (d, J ¼ 8.5 Hz, 1H), 5.20–4.98 (m, 2H), 4.02 (dd, J ¼ 9.5 and 8.5 Hz, 1H), 3.65–
3.31 (m, 1H), 2.17 (s, 3H), 1.77–1.71 (m, 3H), 1.28 (m, 1H). LR MS: 352 (M þ Hþ, 100).
The (3H)-furanones 13e and 13f were unstable and could not be isolated by
liquid chromatography. The subsequent reactions with triethylamine were carried
out on the crude reaction products.
Preparation of (Z)-1-Phenyl-3-cyano-2-propen-1-ones 14a–f
The reactions were carried out using the procedure reported for the prep-
aration of compound 6, starting from either the crude reaction products or the
purified (3H)-furanones.

2132
H. TRABULSI AND G. ROUSSEAU
(Z)-2-Methyl-4-oxo-4-phenylbut-2-enenitrile 14a. Oil: 60%. 1H NMR
(CDCl3, 360 MHz) d (ppm): 8.09–7.19 (m, 6H), 2.33 (d, J ¼ 1.7 Hz, 3H). 13C
NMR (CDCl3, 62.9 MHz) d: 189.4, 136.7, 136.6, 129.9 (2C), 129.5 (3C), 123.8,
119.2, 17.6. IR (CH2Cl2) t (cmꢁ1): 3063, 2928, 2221, 1667, 1600, 1597, 1449, 1241,
985, 695. HR MS: calculated for C11H10NO (M þ Hþ): 172.0762. Found: 172.0762.
(Z)-2-Ethyl-4-oxo-4-phenylbut-2-enenitrile 14b. Oil: 65%. 1H NMR (CDCl3,
360 MHz) d (ppm): 7.57–7.15 (m, 6H), 3.30 (q, J ¼ 7.1 Hz, 2H), 1.48 (s, 3H). 13C
NMR (CDCl3, 62.9 MHz) d: 193.5, 147.0, 133.8, 129.6, 128.8 (2C), 128.2 (2C),
126.3, 108.5, 38.1, 14.8. IR (CH2Cl2) t (cmꢁ1): 3289, 2923, 2218, 1763, 1689, 1597,
1449, 1329, 1212, 988, 754. HR MS: calculated for C12H12NO (M þ Hþ):
186.0919. Found: 186.0921.
(Z)-2-Benzyl-4-oxo-4-phenylbut-2-enenitrile 14c. Oil: 57%. 1H NMR
(CDCl3, 250MHz) d (ppm): 7.27–8.05 (m, 11H), 4.11 (s, 2H). 13C NMR (CDCl3,
62.9MHz) d: 194.3, 147.1, 133.7 (2C), 130.3 (2C), 128.7 (4C), 128.5 (4C), 128.4, 116.2,
44.5. IR (CH2Cl2) t (cmꢁ1): 2923, 2852, 2211, 1767, 1687, 1580, 1449, 1334, 1213,
997, 754. HR MS: calculated for C17H14NO (M þ Hþ): 248.1075. Found: 248.1079.
(Z)-2-(2-Oxo-2-phenylethylidene)hex-5-enenitrile 14d. Oil: 55%. 1H NMR
(CDCl3, 360 MHz) d (ppm): 7.53–7.17 (m, 6H), 6.00–5.71 (m, 1H), 5.16–4.90 (m,
2H), 2.31–2.00 (m, 3H), 1.84–1.58 (m, 1H). 13C NMR (CDCl3, 75.5 Hz) d (ppm):
195.9, 147.3, 138.2, 131.2, 129.9 (2C), 128.7, 128.4 (2C), 126.3, 114.9, 100.0, 30.3
(2C). IR (CH2Cl2) t (cmꢁ1): 2832, 2756, 2321, 1770, 1696, 1610, 1355, 1336, 1115,
969, 760. HR MS: calculated for C14H17N2O ðM þ NHþ4 Þ: 229.1341. Found:
229.1343.
(Z)-Methyl 3-cyano-5-oxo-5-phenylpent-3-enoate 14e. Oil: 55%. 1H NMR
(CDCl3, 250 MHz) d (ppm): 7.90–7.40 (m, 6H), 3.70 (s, 3H), 3.25 (m, 2H). 13C NMR
(CDCl3, 62.9 MHz) d: 191.2, 170.5, 145.1, 140.2, 128.5 (2C), 128.8, 128.1 (2C), 125.2,
113.8, 52.4, 36.8. HR MS: calculated for C13H15N2O3 ðM þ NHþ4 Þ: 247.1083.
Found: 247.1087.
(Z)-4-Oxo-2,4-diphenylbut-2-enenitrile 14f[17]. Yield 90%. White solid, mp
1
94–96 ꢀC (lit.[17a] mp 95–96 ꢀC). H NMR (CDCl3, 360 MHz) d: 8.18–8.04 (m, 2H),
7.94 (s, 1H), 7.86–7.82 (m, 2H), 7.70–7.65 (m, 1H), 7.60–7.50 (m, 5H).
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