Preparation of α-functionalized alkenylmagnesium reagents via a halide-magnesium exchange

Article abstract of DOI:10.1016/S0040-4020(02)00439-8

A general preparation of alkenylmagnesium derivatives bearing an electron-withdrawing function in the α-position (Y=CN, CO₂R, CONR₂, SO₂Ph) has been made possible by using a low temperature (-40 to -30°C) bromine-magnesium exchange with i-PrMgBr in THF. This reaction has also been used to prepare 5-magnesiated-1,3-dioxin-4-one derivatives bearing an alkoxy substituent in β-position to the carbon-magnesium bond.

Full text of DOI:10.1016/S0040-4020(02)00439-8

TETRAHEDRON
Pergamon
Tetrahedron 58 *2002) 4787±4799
Preparation of a-functionalized alkenylmagnesium reagents via a
halide±magnesium exchange
p
 à Â
Jerome Thibonnet, Viet Anh Vu, Laurent Berillon and Paul Knochel
È È È
Department Chemie, Ludwig-Maximilians-Universitat Munchen, Butenandtstrasse 5-13, D-81377 Munchen, Germany
Received 20 March 2002; accepted 23 April 2002
AbstractÐA general preparation of alkenylmagnesium derivatives bearing an electron-withdrawing function in the a-position *YˆCN,
CO2R, CONR2, SO2Ph) has been made possible by using a low temperature *240 to 2308C) bromine±magnesium exchange with i-PrMgBr
in THF. This reaction has also been used to prepare 5-magnesiated-1,3-dioxin-4-one derivatives bearing an alkoxy substituent in b-position
to the carbon±magnesium bond. q 2002 Published by Elsevier Science Ltd.
1. Introduction
1). The reaction sequence is quite general and electron-with-
drawing groups such as YˆCN, CO2R, or SO2R facilitate
the bromine±magnesium exchange considerably.
Functionalized arylmagnesium compounds are readily
prepared by an iodine±magnesium exchange.1 The reaction
proceeds at low temperature *2308C) if the aromatic ring
bears electron-withdrawing substituents. Similarly, for
alkenyl iodides or bromides, a fast halogen±magnesium
exchange is observed if an electron-withdrawing groupis
attached to the double bond.2 Recently, we report some
examples of alkenylmagnesium compounds bearing an
electron-withdrawing function at the sp2-carbon atom
attached to magnesium.3 Herein, we wish to report our
full results on this topic. The inductive effect of the func-
tional groupis important, such that in most cases, func-
tionalized alkenyl bromides of type 1 can be used for the
generation of the Grignard reagents 2 *Scheme 1).
2. Results and discussion
First, we examined 2-bromonitriles 1a and 1b as precursors
for the bromine±magnesium exchange. These nitriles were
prepared in two or three steps from the cinnamonitrile *4)
and 4-heptanone *5). Thus, the bromination of 4 in CHCl3
furnished the dibromide 64 in 76% yield. In the presence of
piperidine in ethanol,5 an elimination of hydrobromic acid
furnished the desired bromonitrile 1a6 as an E/Z mixture in
84% yield *Scheme 2).
The unsaturated nitrile 7 was obtained by the condensation
of acetonitrile and 4-heptanone *5) in the presence of KOH.7
After bromination and piperidine mediated elimination,
the bromonitrile 1b was obtained in 82% yield. Both of
these cyano-substituted alkenyl bromides underwent a fast
Most exchange reactions occurred between 2508C and
2408C and were complete within 1±12 h. The resulting
alkenylmagnesium compounds reacted well with a range
of electrophiles E1 leading to products of type 3 *Scheme
Scheme 1.
Keywords: magnesium; functionalized Grignard reagents; nitrile; sulfone.
Corresponding author. Tel.: 149-89-2180-7681; fax: 149-89-2180-
7680; e-mail: paul.knochel@cup.uni-muenchen.de
p
Scheme 2.
0040±4020/02/$ - see front matter q 2002 Published by Elsevier Science Ltd.
PII: S0040-4020*02)00439-8

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J. Thibonnet et al. / Tetrahedron 58 ,2002) 4787±4799
Table 1. Products of type 10, 11 obtained by the reaction of a-cyano alkenylmagnesium reagents 8, 9 with various electrophiles
Entry
1
Grignard reagent
Electrophile
Product of type 10, 11
Yield *%)a
77b
8
8
10a *90:10)
2
PhCHO
65
10b *92:8)
3
4
5
8
8
8
PhCOCl
63c
53
47
10c 60:40
10d *70:30)
10e *50:50)
6
7
9
9
RˆH
11a: RˆH
92b
82c
RˆCO2Et
11b: RˆCO2Et
8
9
9
9
Me3SiCl
Bu3SnCl
11c: RˆSiMe3
11d: RˆSnBu3
93
48
R1CHO
10
11
9
9
R1ˆPh
11e: R1ˆPh
67
76
R1ˆE-propenyl
11f R1ˆE-propenyl
12
13
9
9
PhCOCl
o-BrC6H4COCl
11g: RˆPh
68c
58c
11h: Rˆo-BrC6H4
a
Isolated yield of analytically pure product.
The reaction with allyl bromide was catalyzed by CuCN *10 mol%).
Stoichiometric amount of CuCN´2LiCl was used.
b
c

J. Thibonnet et al. / Tetrahedron 58 ,2002) 4787±4799
4789
occurred within 3±4 h at 2358C, affording the magnesium
reagents 15a,b *Table 2).
As was observed for the magnesium organometallics
bearing a cyano groupat the a-position, these reagents
reacted smoothly with aldehydes *entries 4 and 9 of Table
2) and Bu3SnCl *entry 3). In the presence of catalytic
amounts of CuCN *10 mol%), allylic bromides reacted
well, leading to the expected allylated products of type 16
and 17 in satisfactory yields *45±87%; entries 1, 2, 8 and
14). After stoichiometric transmetalation of 14 and 15a,b
with CuCN 2LiCl, the reaction with various acid chlorides
furnished a range of unsaturated 1,3-ketoesters and keto-
amides *entries 5±7, 10±12). Interestingly, direct reaction
of the Grignard reagents 15a,b with b,b-dimethylacryloyl
chloride at 2408C, followed by heating for 3 h at 358C,
provided the cyclohexenone derivatives 18a,b in 52±61%
yield *Scheme 4). The reaction proceeded via the
highly unsaturated intermediate 19, which underwent an
electrocyclization, leading to the 3-methylcyclohexenones
18a,b.
Scheme 3.
bromine±magnesium exchange at 2408C within 15±30 min
providing the desired organomagnesium compounds 8 and 9
*Table 1). These Grignard reagents have reacted smoothly
with a range of electrophiles leading to the products 10a±e
and 11a±h. Aldehydes and ketones, as well as Me3SiCl and
Bu3SnCl, reacted directly with the alkenylmagnesium
species. The products of type 10 were obtained as E/Z
mixtures. For the reaction of 8 or 9 with allylic bromides,
the addition of a catalytic amount of CuCN *10 mol%)
considerably improved the yield *entries 1 and 6). In the
case of the reaction with acyl chlorides, a stoichiometric
transmetalation of the magnesium organometallic with
CuCN´2LiCl,8 a THF soluble copper salt, was performed
*entries 3, 12 and 13). The variable E/Z ratio obtained for
products of type 10 indicated that the intermediate Grignard
species 8 was not con®gurationally stable or did not react
stereoselectively with electrophiles. In order to get an
insight into the nature of the structure of 8, we have
recorded a 13C NMR spectrum of this Grignard reagent in
THF-d8 at 2358C. We have found a chemical shift of
129.6 ppm for CN, which is very similar to the chemical
shift of the bromonitrile *1a: 115.9 ppm). This suggests that
the CN grouphas a triple bond character and that the mag-
Next, we examined the preparation of a-magnesiated
unsaturated sulfones. Styryl phenyl sulfone was treated
with bromine followed by piperidine in re¯uxing cyclo-
hexane, affording 1-bromo-2-phenylethenyl phenyl sulfone
*1f) according to a literature procedure.16 A rapid Br/Mg-
exchange took place in THF at 2458C within 1 h furnishing
the corresponding Grignard reagent 20. Its reaction with
various electrophiles, such as allylic bromides, Me3SiCl,
aldehydes and acid chlorides, provided unsaturated sulfones
of type 21 *Table 3). Remarkably, all products 21a±g were
formed stereoselectively as the E-isomer. As observed with
the magnesium reagents previously studied, copper*I) cata-
lysis was necessary for reaction with allylic bromides
*entries l and 2) and the reactions with acid chlorides
required transmetalation with stoichiometric amounts of
copper*I) salt *entry 6 and 7 of Table 3). Since the
bromine±magnesium exchange occurred so fast, we envi-
sioned the possibility of preparing alkenylmagnesium
halides bearing an oxygen functionality at the b-position.
Usually, for molecules of the general type 22, a fast b-elimi-
nation is observed.17 Few lithium or magnesium organo-
metallics bearing an oxygen function at the b-position are
known.18 We expected that the cyclic systems of type 23
would have a moderate tendency to undergo elimination.
We anticipated that the sensitive organomagnesium deriva-
tives could be obtained by a fast iodine±magnesium
exchange starting from 5-iodo-1,3-dioxin-4-one derivatives
of type 24 *Scheme 5). The iodination of the 1,3-dioxin-4-
ones 25a,b with N-iodosuccinimide in acetic acid19
provided the desired 5-iodo-1,3-dioxin-4-ones 24a,b in
70±85% yield. The reaction of 24a,b with i-PrMgCl in
THF at 2308C for 0.5 h furnished the corresponding
magnesium species 23a,b in 85±90% yield as determined
by GC-analysis of reaction mixture aliquots. The half-lives
of 23a,b were estimated to be 2 and 1 h respectively at
2308C. After reaction with various electrophiles, products
of type 26 were obtained in 57±83% yield *Scheme 6 and
Table 4).
nesium atom is attached to the carbon atom of the nitrile
grouprather than to the nitrogen atom.
9,10
Next, we have
examined the behavior of a-bromoesters and amides 1c±e.
The bromoester 1c11,12 was prepared starting from the acid
chloride 12 by the reaction with LiOt-Bu in THF at 2408C,
leading to t-butyl b,b-dimethylacrylate13, which was bromi-
nated *Br2, CHCl3, 08C) and heated with piperidine at re¯ux
for 12 h to give the bromoester 1c in an overall yield of 48%
*Scheme 3). The treatment of the acid chloride 12 with
Et2NH furnished N,N-diethyl b,b-dimethylacrylate,14
which was brominated and treated as above with piperidine,
inducing the elimination of HBr and leading to the
a-bromoamide 1d in 56% overall yield. The a-bromo-
acid chloride 1315 could be directly converted to the corre-
sponding amide 1e in 86% yield by the reaction with diallyl-
amine in CH2Cl2 at 2408C *Scheme 3). The bromoester 1c
was best magnesiated by reaction with i-PrMgBr
*1.5 equiv.) in THF at 2308C *12 h) leading to the Grignard
reagent 14. The bromoamides 1d,e reacted faster with
As with the magnesium species described above, a direct
reaction was observed with aldehydes *entries 1, 2, 7 and 8
i-PrMgBr *1.1 equiv.).
A complete Br/Mg-exchange

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J. Thibonnet et al. / Tetrahedron 58 ,2002) 4787±4799
Table 2. Products of type 16, 17 obtained by the reaction of a-carbonyl alkenylmagnesium reagents 14, 15 with various electrophiles
Entry
1
Grignard reagent
Electrophile
Product of type 16, 17
Yield *%)a
45b
2Et
14
16a: RˆH
2
3
14
14
16b: RˆCO2Et
65b
53
Bu3SnCl
16c
16d
4
14
PhCHO
ROCl
72
5
6
7
14
14
14
RˆPh
16e: RˆPh
82c
81c
86c
Rˆo-BrC6H4
RˆE-1-pentenyl
16f: Rˆo-BrC6H4
16g: RˆE-1-pentenyl
8
74c
15a
15a
17a
17b
9
PhCHO
76
10
11
15a
15a
PhCOCl
o-BrC6H4COCl
17c: RˆPh
75c
82c
17d: Rˆo-BrC6H4
12
13
15a
17e: RˆE-1-pentenyl
72c
92
H2O
15b
17f
14
87b
17g
a
Isolated yield of analytically pure product.
The reaction with allyl bromide was catalyzed by CuCN *10 mol%).
Stoichiometric amount of CuCN´2LiCl was used.
b
c

J. Thibonnet et al. / Tetrahedron 58 ,2002) 4787±4799
4791
Scheme 5.
expected cross-coupling products 28a±c in 54±57%
*Scheme 7).
Scheme 4.
of Table 4), Me3SnCl *entry 4) and PhSSPh *entry 5). The
copper reagent obtained from 23a,b by transmetalation with
CuCN 2LiCl reacted well with acid chlorides *entry 3).
Reaction with allylic bromides in the presence of a catalytic
amount of a copper*I) salt was possible and led to the allyl-
ated products 26f *81%) and 26i *77%) *see entries 6 and 9).
Finally, the transmetalation of 23a,b to the corresponding
zinc reagents with zinc bromide provided organometallic
compounds *27a,b), which were stable at 608C for several
hours. These reacted with aromatic or alkenyl iodides in the
presence of Pd*dba)2 *5 mol%) and tris-o-furylphosphine
*tfp; 10 mol%) in THF *608C, 12 h)20 and furnished the
3. Conclusion
In summary, we have shown that various alkenyl bromides
of type 1 undergo a fast Br/Mg-exchange providing the
corresponding magnesiated species. Electron-withdrawing
groups like YˆCN, CO2t-Bu, CONR2 and SO2Ph con-
siderably facilitated the rate of exchange and allowed an
ef®cient preparation of polyfunctional alkenylmagnesium
compounds. This mild halogen±magnesium exchange has
been applied to the preparation of 5-magnesiated-1,3-
dioxin-4-one derivatives bearing an alkoxy substituent at
b-position to the carbon±magnesium bond.
Table 3. Products of type 21 obtained by the reaction of the a-sulfonyl alkenylmagnesium reagents 20 with various electrophiles
Entry
Grignard reagent
Electrophile
Product of type 21
Yield *%)a
1
76b
20
20
RˆH
21a: RˆH
2
3
RˆCO2Et
21b: RˆCO2Et
59b
82
20
20
20
Me3SiCl
21c
21d
21e
4
5
PhCHO
67
64
6
7
20
20
PhCOCl
p-MeOC6H4COCl
21f: RˆPh
62c
67c
21g: Rˆp-MeOC6H4
a
Isolated yield of analytically pure product.
The reaction with allyl bromide was catalyzed by CuCN *10 mol%).
Stoichiometric amount of CuCN´2LiCl was used.
b
c

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J. Thibonnet et al. / Tetrahedron 58 ,2002) 4787±4799
Scheme 6.
Table 4. 5-Substituted 1,3-dioxin-4-ones of type 26 obtained by the reaction of the magnesiated 1,3-dioxin-4-ones 23a,b with various electrophiles
Entry
Grignard reagent
Electrophile
Product of type 26
Yield *%)a
1
2
23a
23a
PhCHO
c-HexCHO
26a:RˆPh
81
64
26b:Rˆc-Hex
3
23a
PhCOCl
83b
26c
4
5
23a
23a
Me3SnCl
PhSSPh
26d:RˆSnMe3
26e:RˆSPh
59
68
6
23a
Allyl bromide
81c
26f
7
8
23b
23b
PhCHO
c-HexCHO
26g:RˆPh
76
57
26h:Rˆc-Hex
9
10
23b
23b
Allyl bromide
Ethyl *2-bromomethyl) acrylate
26i:RˆH
77b
65b
26j:RˆCO2Et
a
Isolated yield of analytically pure product.
Reaction performed after a transmetalation to the corresponding copper reagent by adding CuCN´2LiCl *1.0 equiv.).
Reaction performed in the presence of CuCN´2LiCl *10 mol%).
b
c

J. Thibonnet et al. / Tetrahedron 58 ,2002) 4787±4799
4793
Scheme 7.
1
4. Experimental
1077 *m), 965 *s) cm21. H NMR *CDCl3, 300 MHz): d
5.72 *dq, Jˆ16.6, 6.3 Hz, 1H), 5.56 *dd, Jˆ16.6, 6.3 Hz,
1H), 4.87 *d, Jˆ6.3 Hz, 1H), 2.78 *bs, 1H), 2.30 *t, Jˆ
6.9 Hz, 2H), 2.16±2.09 *m, 2H), 1.66 *dd, Jˆ6.3, 0.9 Hz,
3H), 1.50±1.36 *m, 4H), 0.89 *t, Jˆ7.2 Hz, 3H), 0.87 *t,
Jˆ7.2 Hz, 3H). 13C NMR *CDCl3, 75 MHz): d 162.5,
131.5, 129.8, 118.5, 115.4, 69.6, 39.4, 34.8, 22.8, 22.7,
18.8, 15.3, 15.0. m/z *EI-MS): 207 *4), 192 *15), 178 *49),
164 *50), 150 *29), 136 *25), 122 *43), 94 *34), 81 *42).
HRMS: calcd for C13H21NO 207.1623, found: 207.1622.
4.1. General methods
Unless otherwise indicated, all reactions were carried out
under an argon atmosphere. THF, Et2O and t-butyl methyl
ether *TBME) were distilled from sodium/benzophenone,
CH2Cl2 and DMF from CaH2. Reactions were monitored
by gas chromatography *GC) analysis of worked up reaction
aliquots. Analytical thin-layer chromatography *TLC) was
performed using Merck silica gel *60 F-254) plates
*0.25 mm) precoated with a ¯uorescent indicator. Column
chromatography was carried out on silica gel 60 *70±230
mesh). NMR data were recorded on a 300 MHz NMR
spectrometer. The ionization method used was electron
impact ionization *EI, 70 eV). Melting points are uncor-
rected. Elemental analyses were performed by the Micro-
4.2.2. 2-Benzylidene-pent-4-enenitrile /10a). The reaction
was carried out according to typical procedure A. IR *neat):
3083 *w), 3027 *w), 2940 *w), 2211 *s), 1640 *m), 1597 *w),
1574 *w), 1448 *m), 1233 *m), 992 *m), 927 *s), 752 *s), 693
*s) cm21. H NMR *CDCl3, 300 MHz): d 7.66±7.62 *m,
1
2H), 7.32±7.21 *m, 3H), 6.87 *s, 1H), 5.90±5.75 *m, 1H),
5.21±5.14 *m, 2H), 3.11 *dt, Jˆ4.5, 1.5 Hz, 2H), 3.05 *dt,
Jˆ4.0, 1.2 Hz). 13C NMR *CDCl3, 75 MHz): d 144.4,
133.2, 131.3, 130.5, 129.4, 129.2, 129.0, 119.2, 109.9,
40.4. m/z *EI-MS): 168 *80), 154 *100), 141 *37), 115
*30). HRMS: calcd for C12H11N 169.0891, found: 169.0893.
È
È
analytical Service Laboratory of Universitat Munchen.
4.2. Starting materials
The following starting materials were prepared according to
literature procedures: 1a, 1b4,5 1c,13 1d,14 1e,15 1f,16 25a,
24a,b.19
4.2.3. 2-/Hydroxy-phenyl-methyl)-3-phenyl-acrylonitrile
/10b). The reaction was carried out according to typical
procedure A. IR *neat): 3435 *s), 3087 *w), 3062 *m),
3030 *m), 2216 *s), 1957 *w), 1810 *w), 1623 *s), 1576
*m), 1494 *s), 1450 *s), 1397 *m), 1236 *m), 1192 *m),
4.2.1. Typical procedure A. 2-/1-Hydroxy-but-2-enyl)-3-
propyl-hex-2-enenitrile /11f). A solution of i-PrMgBr
*4.1 mmol) in THF *0.80 M, 5.1 mL) was added dropwise
over 5 min to a stirred solution of the bromonitrile 1a
*800 mg, 3.7 mmol) in THF *5 mL) at 2408C under
argon. The resulting solution was then stirred for 30 min
and crotonaldehyde *400 mL, 4.8 mmol) was added. The
reaction mixture was allowed to warm to room temperature,
brine was added and the reaction mixture was worked upas
usual. The crude residue was puri®ed by column chroma-
tography on silica to give 11f *583 mg, 76%) as a colorless
oil. IR *neat): 3440 *vs), 3028 *w), 2963 *s), 2935 *s), 2874
*m), 2214 *m), 1673 *w), 1622 *m), 1456 *m), 1380 *w),
1043 *s), 728 *s), 691 *s) cm21
.
1H NMR *CDCl3,
300 MHz): d 7.56±7.53 *m, 2H), 7.25±7.11 *m, 9H), 5.20
*s, 1H), 3.45 *bs, 1H). 13C NMR *CDCl3, 75 MHz): d 143.4,
140.4, 133.5, 131.1, 129.7, 129.6, 129.3, 129.1, 127.0,
117.9, 114.9, 75.8. m/z *EI-MS): 235 *58), 206 *15), 130
*80), 105 *100), 77 *60), 51 *14). HRMS: calcd for
C16H13NO 251.1885, found: 235.0988.
4.2.4. 2-Benzoyl-3-phenyl-acrylonitrile /10c). The reac-
tion was carried out according to typical procedure A. IR

4794
J. Thibonnet et al. / Tetrahedron 58 ,2002) 4787±4799
*neat): 3051 *m), 2230 *w), 1704 *m), 1650 *s), 1596 *m),
1571 *m), 1449 *m), 1324 *m), 1267 *m), 701 *w) cm21. 1H
NMR *CDCl3, 300 MHz): d 8.17±8.13 *m, 1H), 8.08±8.03
*m, 2H), 7.94±7.90 *m, 1H), 7.66±7.47 *m, 7H). 13C NMR
*CDCl3, 75 MHz): d 189.4, 172.6, 156.0, 136.2, 134.2,
133.9, 132.2, 131.5, 130.6, 130.2, 129.1, 128.9, 117.3,
110.6. m/z *EI-MS): 233 *71), 206 *9), 105 *100), 77 *51),
51 *11). HRMS: calcd for C16H11NO 233.0841, found:
233.0839.
Jˆ7.5 Hz, 2H), 2.12 *t, Jˆ7.8 Hz, 2H), 1.50±1.33 *m, 4H),
1.23 *t, Jˆ7.2 Hz, 3H), 0.88 *t, Jˆ7.2 Hz, 3H), 0.86 *t,
Jˆ7.5 Hz, 3H). 13C NMR *CDCl3, 75 MHz): d 166.5,
162.8, 136.9, 127.0, 119.1, 107.2, 61.3, 38.3, 33.8, 32.2,
22.0, 21.7, 14.4, 14.1. m/z *EI-MS): 249 *56), 220 *34),
204 *24), 188 *31), 175 *100), 165 *59), 146 *83), 132
*86), 118 *44), 104 *81), 91 *44), 77 *88). HRMS: calcd
for C15H23NO2 249.1729, found: 249.1711.
4.2.9. 3-Propyl-2-trimethylsilyl-hex-2-enenitrile /11c).
The reaction was carried out according to typical procedure
A. IR *neat): 2962 *s), 2934 *m), 2874 *m), 2195 *m), 1575
4.2.5. 2-[1-Hydroxy-1-/4-methoxy-phenyl)-ethyl]-3-phenyl-
acrylonitrile /10d). The reaction was carried out according
to typical procedure A. A 70:30 mixture of isomers was
isolated. IR *neat): 3450 *s), 3059 *w), 3029 *w), 2980
*m), 2935 *m), 2213 *s), 1959 *w), 1893 *w), 1661 *m),
1609 *s), 1583 *m), 1512 *s), 1252 *s), 1179 *s), 1103 *m),
1032 *s), 833 *s) cm21. Isomer 1: 1H NMR *CDCl3,
300 MHz): d 7.67±7.65 *m, 2H), 7.37±7.29 *m, 6H), 6.82
*d, Jˆ9 Hz, 2H), 3.72 *s, 3H), 2.31 *bs, 1H), 1.85 *s, 3H).
13C NMR *CDCl3, 75 MHz): d 159.8, 141.5, 136.3, 133.6,
130.7, 129.5, 129.2, 127.4, 119.7, 118.2, 114.4, 75.7, 55.7,
1
*m), 1467 *m), 1254 *s), 843 *s) cm21. H NMR *CDCl3,
300 MHz): d 2.21 *t, Jˆ7.8 Hz, 2H), 1.96 *t, Jˆ7.8 Hz, 2H),
1.30±1.15 *m, 4H), 0.69 *t, Jˆ7.2 Hz, 3H), 0.68 *t, Jˆ
7.2 Hz, 3H), 0.0 *s, 9H). 13C NMR *CDCl3, 75 MHz): d
183.5, 125.3, 114.1, 44.4, 42.9, 27.0, 26.8, 19.2, 19.0, 5.0.
m/z *EI-MS): 209 *11), 195 *24), 194 *100), 181 *12), 166
*22), 153 *66), 126 *14), 125 *25), 84 *25), 74 *11), 73 *98),
59 *23), 45 *11. HRMS: calcd for C12H23NSi 209.1600,
found: 209.1583.
1
28.9. Isomer 2: H NMR *CDCl3, 300 MHz): d 7.33 *d,
Jˆ9 Hz, 2H), 7.29 *s, 1H), 7.15±7.05 *m, 5H), 6.76 *d,
Jˆ9 Hz, 2H), 3.70 *s, 3H), 2.45 *bs, 1H), 1.73 *s, 3H). 13C
NMR *CDCl3, 75 MHz): d 159.5, 146.5, 138.3, 134.2,
129.7, 128.6, 126.7, 124.0, 120.4, 114.3, 75.2, 55.7, 32.4.
m/z *EI-MS): 279 *29), 264 *14), 151 *100), 135 *42), 77
*16). HRMS: calcd for C18H17NO2 279.1259, found:
279.1264.
4.2.10. 3-Propyl-2-tributylstannyl-hex-2-enenitrile /11d).
The reaction was carried out according to typical procedure
A. IR *neat): 2959 *s), 2872 *s), 2184 *s), 1613 *w), 1576
*m), 1464 *m), 1378 *m), 1075 *w) cm21. 1H NMR *CDCl3,
300 MHz): d 2.43 *d, Jˆ7.8 Hz, 2H), 2.05 *t, Jˆ7.6 Hz,
2H), 1.50±1.23 *m, 12H), 1.05±1.00 *m, 6H), 0.90±0.80
*m, 15H). 13C NMR *CDCl3, 75 MHz): d 175.9, 120.3,
106.8, 40.1, 37.7, 27.8, 26.9, 20.8, 20.6, 13.1, 12.8, 12.6,
10.3. m/z *EI-MS): 426 *15), 370 *100), 314 *43), 258 *55),
189 *16), 177 *19), 121 *17), 55 *10). HRMS: calcd for
C21H41NSn 425.2261, found: 425.2281.
4.2.6. 2-Benzylidene-3-hydroxy-hex-4-enenitrile /10e).
The reaction was carried out according to typical procedure
A. IR *neat): 3436 *s), 3030 *m), 2973 *m), 2918 *m), 2216
*s), 1698 *m), 1623 *m), 1449 *s), 1293 *m), 1211 *m), 1076
*s), 966 *s) cm21. 1H NMR *CDCl3, 300 MHz): d 7.68±7.64
*m, 2H), 7.33±7.18 *m, 3H), 7.13 *d, Jˆ0.6 Hz, 1H), 5.85±
5.75 *m, 1H), 5.54 *dd, Jˆ15.3, 6.9 Hz, 1H), 4.72 *bd, Jˆ
5.1 Hz, 1H), 2.65 *bs, 1H), 1.68 *dd, Jˆ9.6, 0.6 Hz) 13C
NMR *CDCl3, 75 MHz): d 143.0, 133.6, 131.4, 130.9,
129.8, 129.7, 129.2, 117.9, 114.1, 74.7, 18.2. m/z *EI-MS):
198 *100), 180 *22), 170 *47), 154 *32), 140 *22), 129 *63),
115 *21), 102 *34), 91 *22), 78 *91). HRMS: calcd for
C13H13NO 199.0997, found: 199.0996.
4.2.11. 2-/Hydroxy-phenyl-methyl)-3-propyl-hex-2-ene-
nitrile /11e). The reaction was carried out according to
typical procedure A. IR *neat): 3436 *vs), 3088 *w), 3063
*w), 3030 *w), 2963 *s), 2933 *m), 2873 *m), 2214 *m), 1619
1
*m), 1454 *m), 1040 *s), 1025 *s), 728 *s), 699 cm21. H
NMR *CDCl3, 300 MHz): d 7.46±7.32 *m, 5H), 5.62 *s,
1H), 2.85 *bs, 1H), 2.43 *t, Jˆ7.8 Hz, 2H), 2.29 *t, Jˆ
8.1 Hz, 2H), 1.58±1.47 *m, 4H), 0.98 *t, Jˆ7.2 Hz, 3H),
0.97 *t, Jˆ7.2 Hz, 3H). 13C NMR *CDCl3, 75 MHz): d
162.2, 141.4, 129.1, 128.6, 126.4, 117.6, 115.2, 70.0, 38.6,
34.5, 22.0, 14.7, 14.3. m/z *EI-MS): 243 *4), 225 *59), 200
*48), 182 *78), 154 *86), 122 *20), 107 *100), 79 *44).
HRMS: calcd for C16H21NO 243.1623, found: 243.1645.
4.2.7. 2-Allyl-3-propyl-hex-2-enenitrile /11a). The reac-
tion was carried out according to typical procedure A. IR
*neat): 3083 *w), 2963 *s), 2934 *s), 2874 *m), 2209 *m),
1
1641 *m), 1623 *w), 1467 *m), 992 *w), 918 *m) cm21. H
NMR *CDCl3, 300 MHz): d 5.78±5.67 *m, 1H), 5.10±5.03
*m, 2H), 2.89 *d, Jˆ6 Hz, 2H), 2.32 *t, Jˆ7.8 Hz, 2H), 2.07
*t, Jˆ7.8 Hz, 2H), 1.49±1.32 *m, 4H), 0.89 *t, Jˆ7.5 Hz,
3H), 0.86 *t, Jˆ7.5 Hz, 3H). 13C NMR *CDCl3, 75 MHz): d
161.3, 133.8, 119.5, 117.4, 108.1, 38.3, 34.3, 33.7, 22.0,
21.7, 14.5, 14. m/z *EI-MS): 177 *40), 148 *50), 134 *59),
120 *55), 106 *100), 93 *88), 79 *64), 55 *42), 41 *98).
HRMS: calcd for C12H19N 177.1417, found: 177.1535.
4.2.12. 2-Benzoyl-3-propyl-hex-2-enenitrile /11g). The
reaction was carried out according to typical procedure A.
IR *neat): 3065 *w), 2964 *s), 2934 *m), 2874 *m), 2210 *m),
1674 *s), 1598 *m), 1580 *m), 1449 *m), 1249 *s), 901 *m),
1
720 *m) cm21. H NMR *CDCl3, 300 MHz): d 7.95±7.92
*m, 2H), 7.63±7.48 *m, 3H), 2.61 *t, Jˆ7.8 Hz, 2H), 2.33 *t,
Jˆ7.8 Hz, 2H), 1.74±1.67 *m, 2H), 1.56±1.49 *m, 2H), 1.09
*t, Jˆ7.2 Hz, 3H), 0.89 *t, Jˆ7.2 Hz, 3H). 13C NMR *CDCl3,
75 MHz): d 134.5, 129.9, 129.2, 38.7, 35.6, 22.3, 22.1, 14.5,
14.4. m/z *EI-MS): 241 *4), 239 *15), 224 *26), 212 *31), 207
*17), 198 *42), 170 *51), 105 *100), 77 *61), 44 *57). HRMS:
calcd for C16H19NO 241.1467, found: 241.1489.
4.2.8. 4-Cyano-2-methylene-5-propyl-oct-4-enoic acid
ethyl ester /11b). The reaction was carried out according
to typical procedure A. IR *neat): 2964 *s), 2874 *m), 2210
*m), 1716 *vs), 1634 *m), 1467 *m), 1279 *m), 1256 *m),
1152 *s), 1027 *m), 949 *m), 818 *w) cm21
.
*CDCl3, 300 MHz): d 6.24 *m, 1H), 5.57 *m, 1H), 4.15 *q,
1H NMR
4.2.13. 2-/2-Bromo-benzoyl)-3-propyl-hex-2-enenitrile
/11h). The reaction was carried out according to typical

J. Thibonnet et al. / Tetrahedron 58 ,2002) 4787±4799
4795
procedure A. IR *neat): 3067 *w), 2965 *s), 2933 *s), 2874
*m), 2216 *m), 1682 *s), 1588 *s), 1568 *s), 1465 *m), 1430
4.2.18. 2-Benzoyl-3-methyl-but-2-enoic acid tert-butyl
ester /16e). The reaction was carried out according to
typical procedure A. IR *neat): 3062 *w), 2978 *m), 2934
*w), 1716 *s), 1675 *s), 1597 *m), 1582 *w), 1449 *m), 1368
*m), 1289 *m), 1242 *m), 1027 *m), 900 *m), 752 *m) cm21
.
1H NMR *CDCl3, 300 MHz): d 7.62 *d, Jˆ7.5 Hz, 1H),
7.43±7.33 *m, 3H), 2.66±2.56 *m, 4H), 1.74±1.56 *m,
4H), 1.06 *t, Jˆ7.5 Hz, 3H), 0. 97 *t, Jˆ7.4 Hz, 3H). 13C
NMR *CDCl3, 75 MHz): d 189.9, 181.4, 140.4, 133.9,
132.8, 129.7, 128.0, 119.8, 116.9, 112.9, 40.9, 36.5, 22.2,
21.9, 14.8, 14.6. m/z *EI-MS): 320 *11), 290 *36), 276 *31),
240 *37), 211 *63), 198 *58), 183 *100), 169 *17), 76 *23), 50
*10). HRMS: calcd for C16H18BrNO 319.0572, found
319.0575.
*m), 1250 *s), 1159 *s), 1084 *m), 877 *w), 705 *m) cm21
.
1H NMR *CDCl3, 300 MHz): d 7.81 *d, Jˆ8.2 Hz, 1H),
7.50±7.36 *m, 3H), 2.21 *s, 3H), 1.76 *s, 3H), 1.16 *s,
9H). 13C NMR *CDCl3, 75 MHz): d 196.0, 164.4, 154.1,
138.1, 133.4, 131.4, 130.4, 129.1, 128.9, 81.6, 28.4, 24.4,
22.4. m/z *EI-MS): 187 *6), 165 *10), 159 *16), 145 *23), 115
*17), 105 *100), 91 *12), 83 *12), 77 *65), 56 *33). HRMS:
calcd for C16H20O3 260.1412, found: 260.1405.
4.2.14. 2-Isopropylidene-pent-4-enoic acid tert-butyl
ester /16a). The reaction was carried out according to
typical procedure A. IR *neat): 3080 *w), 2978 *m), 2931
*w), 1710 *vs), 1638 *w), 1455 *w), 1367 *m), 1285 *m),
4.2.19. 2-/2-Bromobenzoyl)-3-methyl-but-2-enoic acid
tert-butyl ester /16f). The reaction was carried out accord-
ing to typical procedure A. IR *neat): 3065 *w), 2978 *m),
2932 *w), 1719 *vs), 1683 *s), 1622 *m), 1586 *m), 1430
*m), 1368 *m), 1275 *s), 1250 *s), 1161 *s), 1084 *m), 741
1166 *vs), 1112 *m), 910 *w) cm21 1H NMR *CDCl3,
.
1
300 MHz): d 5.77 *ddt, Jˆ17, 10, 7.1 Hz, 1H), 5.05±4.93
*m, 2H), 3.02 *bd, Jˆ7.1 Hz, 2H), 1.89 *s, 3H), 1.70 *s, 3H),
1.41 *s, 3H). 13C NMR *CDCl3, 75 MHz): d 169.2, 141.7,
136.0, 127.2, 115.3, 80.5, 34.7, 28.6, 23.1, 22.0. m/z
*EI-MS): 140 *100), 125 *40), 123 *40), 95 *19), 57 *24).
HRMS: calcd for C12H20O2 196.1413, found: 196.1467.
*m) cm21. H NMR *CDCl3, 300 MHz): d 7.35 *d, Jˆ
8.2 Hz, 1H), 7.26 *d, Jˆ8.1 Hz, 1H), 7.03 *m, 2H), 1.95
*s, 3H), 1.78 *s, 3H), 0.92 *s, 9H). 13C NMR *CDCl3,
75 MHz): d 193.7, 165.0, 157.6, 140.2, 134.6, 132.6,
132.4, 130.6, 127.4, 121.1, 81.8, 28.0, 24.2, 23.7. m/z
*EI-MS): 339 *3), 265 *20), 203 *100), 185 *33), 57 *13).
HRMS: calcd for C16H19O3Br 338.0518, found: 338.0520.
4.2.15. 2-Isopropylidene-4-methylene-pentanedioic acid
1-tert-butyl ester 5-ethyl ester /16b). The reaction was
carried out according to typical procedure A. IR *neat):
2979 *m), 2934 *w), 1715 *vs), 1633 *w), 1455 *w), 1368
*m), 1276 *m), 1229 *m), 1163 *s), 1144 *s), 1079 *m), 1029
4.2.20. 2-Isopropylidene-3-oxo-oct-4-enoic acid tert-
butyl ester /16g). The reaction was carried out according
to typical procedure A. IR *neat): 2965 *s), 2933 *s), 2874
*m), 1716 *vs), 1682 *m), 1663 *s), 1629 *m), 1457 *m),
1
1
*m) cm21. H NMR *CDCl3, 300 MHz): d 6.12 *m, 1H),
1368 *s), 1250 *s), 1161 *s), 1099 *m), 979 *m) cm21. H
5.43 *m, 1H), 4.14 *q, Jˆ7.2 Hz, 2H), 3.21 *s, 2H), 1.94
*s, 3H), 1.69 *s, 3H), 1.37 *s, 9H), 1.23 *t, Jˆ7.2 Hz, 3H).
13C NMR *CDCl3, 75 MHz): d 168.7, 167.4, 143.3, 138.7,
126.3, 124.8, 80.6, 61.0, 32.1, 28.5, 23.1, 22.3, 14.5. m/z
*EI-MS): 268 *4), 194 *100), 166 *34), 138 *11), 57 *10).
HRMS: calcd for C15H24O4 268.1675, found: 268.1679.
NMR *CDCl3, 300 MHz): d 6.70 *dt, Jˆ15.8, 7.0 Hz, 1H),
6.11 *dt, Jˆ15.8, 1.6 Hz, 1H), 2.15 *dt, Jˆ7.0, 7.1 Hz, 2H),
2.09 *s, 3H), 1.74 *s, 3H), 1.42 *m, 2H), 1.36 *s, 9H), 0.86 *t,
Jˆ7.0 Hz, 3H). 13C NMR *CDCl3, 75 MHz): d 195.5, 164.8,
162.0, 152.1, 150.1, 131.9, 81.5, 34.8, 28.3, 23.9, 22.4, 21.6,
14.4. m/z *EI-MS): 179 *3), 109 *10), 97 *13), 83 *12), 56
*33), 41 *100). HRMS: calcd for C15H24O3 252.1725, found:
252.1714.
4.2.16. 3-Methyl-2-tributylstannyl-but-2-enoic acid tert-
butyl ester /16c). The reaction was carried out according to
typical procedure A. IR *neat): 2957 *s), 2928 *s), 2871 *m),
2854 *m), 1702 *s), 1613 *w), 1455 *m), 1366 *m), 1246 *m),
4.2.21. 4-Diethylcarbamoyl-5-methyl-2-methylene-hex-
4-enoic acid ethyl ester /17a). The reaction was carried
out according to typical procedure A. IR *neat): 2978 *s),
2934 *s), 1715 *s), 1621 *s), 1427 *m), 1275 *m), 1221 *m),
1
1157 *vs), 1082 *m) cm21. H NMR *CDCl3, 300 MHz): d
1.89 *s, 3H), 1.81 *s, 3H), 1.58±1.50 *m, 6H), 1.47 *s, 9H),
1.42±1.21 *m, 6H), 1.00±0.91 *m, 6H), 0.87 *t, Jˆ7.2 Hz,
9H). 13C NMR *CDCl3, 75 MHz): d 173.0, 148.7, 145.0,
80.2, 29.5, 28.7, 27.7, 27.5, 23.1, 14.0, 11.5. m/z *EI-MS):
389 *11), 333 *91), 315 *100), 251 *11), 201 *12), 177 *11).
HRMS: calcd for C21H42O2Sn 444.2207, found: 444.2219.
1
1142 *m), 1027 *w) cm21. H NMR *CDCl3, 300 MHz): d
6.22 *m, 1H), 5.76 *m, 1H), 4.20 *q, Jˆ7.2 Hz, 2H), 3.51±
3.32 *m, 2H), 3.27 *q, Jˆ7.2 Hz, 2H), 1.75 *s, 3H), 1.69 *s,
3H), 1.29 *t, Jˆ7.2 Hz, 3H), 1.14 *t, Jˆ7.2 Hz, 3H), 1.12 *t,
Jˆ7.2 Hz, 3H). 13C NMR *CDCl3, 75 MHz): d 171.7, 167.2,
137.4, 131.9, 128.0, 127.1, 60.9, 42.2, 38.1, 33.2, 22.3, 20.3,
14.5, 14.3, 12.9. m/z *EI-MS): 267 *27), 252 *17), 222 *19),
206 *22), 194 *100), 166 *19), 121 *32), 93 *33), 77 *10).
HRMS: calcd for C15H25NO3 267.1834, found: 267.1809.
4.2.17. 2-/Hydroxy-phenyl-methyl)-3-methyl-but-2-enoic
acid tert-butyl ester /16d). The reaction was carried out
according to typical procedure A. IR *neat): 3450 *vs),
3061 *w), 3028 *w), 2977 *m), 2930 *m), 1719 *vs), 1449
*m), 1368 *m), 1325 *m), 1161 *s), 1089 *m), 1014 *m), 851
4.2.22. 2-/Hydroxy-phenyl-methyl)-3-methyl-but-2-enoic
acid diethylamide /17b). The reaction was carried out
according to typical procedure A. IR *neat): 3350 *vs),
3083 *w), 3061 *w), 2979 *m), 2935 *m), 1655 *m), 1580
*vs), 1455 *s), 1424 *s), 1382 *m), 1019 *m), 746 *m), 703
1
*w), 701 *m) cm21. H NMR *CDCl3, 300 MHz): d 7.39±
7.20 *m, 5H), 5.67 *d, Jˆ10.2 Hz, 1H), 3.58 *d, Jˆ10.2 Hz,
1H), 2.04 *s, 3H), 1.98 *s, 3H), 1.21 *s, 9H). 13C NMR
*CDCl3, 75 MHz): d 168.2, 144.1, 143.6, 131.4, 128.4,
127.2, 126.1, 81.9, 71.2, 28.2, 23.5, 21.8. m/z *EI-MS):
245 *5), 206 *100), 187 *63), 173 *14), 160 *41), 143 *44),
129 *21), 105 *27), 77 *11), 57 *19). HRMS: calcd for
C16H22O3 262.1569, found: 262.1581.
1
*m) cm21. H NMR *CDCl3, 300 MHz): d 7.07±6.90 *m,
5H), 5.52 *s, 1H), 3.07±2.99 *m, 2H), 2.63 *m, 1H), 2.46 *m,
1H), 1.80 *s, 3H), 1.47 *s, 3H), 0.75 *t, Jˆ7.2 Hz, 3H), 0.21
*t, Jˆ7.2 Hz, 3H). 13C NMR *CDCl3, 75 MHz): d 170.9,

4796
J. Thibonnet et al. / Tetrahedron 58 ,2002) 4787±4799
143.4, 132.8, 131.9, 128.7, 127.4, 125.9, 71.7, 42.5, 37.8,
22.9, 19.8, 12.9, 12.6. m/z *EI-MS): 261 *26), 243 *54), 214
*100), 171 *46), 160 *50), 143 *65), 128 *85), 74 *62), 58
*32). HRMS: calcd for C16H23NO2 261.1729, found:
261.1724.
3H), 5.19±4.98 *m, 6H), 4.00 *bs, 2H), 3.86 *d, Jˆ5.4 Hz,
2H), 2.95 *bs, 2H), 1.70 *s, 3H), 1.66 *s, 3H). 13C NMR
*CDCl3, 75 MHz): d 172.6, 135.3, 134.2, 133.3, 131.3,
128.7, 118.5, 118.1, 116.5, 50.5, 45.8, 35.6, 22.5, 19.5.
m/z *EI-MS): 219 *8), 204 *31), 178 *28), 164 *14), 123
*100), 108 *15), 95 *28), 79 *22), 67 *21). HRMS: calcd
for C14H21NO 219.1623, found: 219.1627.
4.2.23. 2-Benzoyl-3-methyl-but-2-enoic acid diethyl-
amide /17c). The reaction was carried out according to
typical procedure A. IR *neat): 3063 *w), 2977 *m), 2936
*m), 2875 *m), 1659 *s), 1598 *s), 1580 *m), 1449 *s), 1428
*s), 1381 *m), 1317 *m), 1283 *s), 1268 *s), 1230 *m), 1069
*m), 843 *m) cm21. 1H NMR *CDCl3, 300 MHz): d 8.00 *d,
Jˆ8.4 Hz, 2H), 7.46±7.33 *m, 3H), 3.40 *q, Jˆ7.2 Hz, 2H),
3.29 *q, Jˆ7.2 Hz, 2H), 1.82 *s, 3H), 1.64 *s, 3H), 1.03 *t,
Jˆ7.2 Hz, 3H), 0.97 *t, Jˆ7.2 Hz, 3H). 13C NMR *CDCl3,
75 MHz): d 195.7, 167.2, 141.6, 137.7, 135.2, 133.7, 130.3,
128.8, 43.1, 39.2, 22.4, 21.9, 14.3, 12.8. m/z *EI-MS): 259
*5), 244 *100), 220 *16), 187 *20), 161 *58), 154 *46), 145
*12), 105 *95), 83 *48), 72 *80). HRMS: calcd for
C16H21NO2 259.1572, found: 259.1575.
4.2.28. 4,6,6-Trimethyl-2-oxo-cyclohex-3-enecarboxylic
acid diethylamide /18a). The reaction was carried out
according to typical procedure A. IR *neat): 2969 *m),
2934 *m), 2873 *w), 1662 *s), 1639 *vs), 1428 *m), 1379
*m), 1270 *m), 1246 *m), 1136 *w) cm21. 1H NMR *CDCl3,
300 MHz): d 5.80 *m, Jˆ1.2 Hz, 1H), 3.55 *m, 1H), 3.33±
3.20 *m, 3H), 3.23 *s, 1H), 3.05 *d, Jˆ18 Hz, 1H), 1.90 *s,
3H), 1.81 *d, Jˆ18.3 Hz, 1H), 1.19 *t, Jˆ7.2 Hz, 3H), 1.10±
0.98 *m, 9H). 13C NMR *CDCl3, 75 MHz): d 196.9, 168.2,
163.1, 124.2, 59.0, 43.7, 43.1, 41.2, 36.3, 29.3, 26.7, 25.0,
15.1, 13.4. m/z *EI-MS): 237 *25), 155 *26), 140 *38), 100
*100), 72 *80), 58 *20). HRMS: calcd for C14H23NO2
237.1729, found: 237.1738.
4.2.24. 2-/2-Bromo-benzoyl)-3-methyl-but-2-enoic acid
diethylamide /17d). The reaction was carried out according
to typical procedure A. IR *neat): 3063 *w), 2976 *m), 2936
*m)0, 2875 *m), 1672 *s), 1621 *vs), 1429 *s), 1381 *m),
1316 *m), 1283 *m), 1220 *m), 1081 *m), 756 *m) cm21. 1H
NMR *CDCl3, 300 MHz): d 7.54±7.48 *m, 2H), 7.25±7.17
*m, 2H), 3.31±3.26 *m, 4H), 1.85 *s, 3H), 1.83 *s, 3H), 1.02
*t, Jˆ7.2 Hz, 3H), 0.84 *t, Jˆ7.2 Hz, 3H). 13C NMR
*CDCl3, 75 MHz): d 193.5, 167.6, 150.4, 140.8, 135.5,
133.9, 131.9, 130.4, 127.4, 119.9, 43.3, 38.9, 24.5, 22.3,
14.4, 12.4. m/z *EI-MS): 322 *18), 258 *100), 183 *66),
157 *12), 72 *42), 58 *11). HRMS: calcd for C16H20NO2Br
337.0677, found: 337.0682.
4.2.29. 4,6,6-Trimethyl-2-oxo-cyclohex-3-enecarboxylic
acid diallylamide /18b). The reaction was carried out
according to typical procedure A. IR *neat): 3082 *w),
2961 *s), 1651 *vs), 1436 *m), 1410 *m), 1243 *m), 1190
*m), 994 *w), 924 *m) cm21. 1H NMR *CDCl3, 300 MHz): d
5.81 *m, Jˆ1.2 Hz, 1H), 5.80±5.60 *m, 2H), 5.18±5.00 *m,
4H), 4.44 *ddt, Jˆ18, 5.2, 1.2 Hz, 1H), 4.13 *ddt, Jˆ15.4,
5.2, 1.2 Hz, 1H), 3.79 *ddt, Jˆ18.2, 5.2, 1.2 Hz, 1H), 3.67
*ddt, Jˆ15.4, 5.2, 1.2 Hz, 1H), 3.26 *s, 1H), 3.05 *d, Jˆ
18.6 Hz, 1H), 1.89 *s, 1H), 1.83 *d, Jˆ18.6 Hz, 1H), 1.04
*s, 3H), 0.96 *s, 3H). 13C NMR *CDCl3, 75 MHz): d 196.7,
169.1, 163.3, 133.7, 133.2, 124.1, 117.2, 117.1, 59.2, 50.1,
48.6, 44.0, 36.3, 29.3, 26.6, 25.0. m/z *EI-MS): 261 *8), 246
*10), 165 *12), 149 *17), 123 *24), 96 *100), 83 *27), 55 *12),
39 *14). HRMS: calcd for C16H23NO2 261.1729, found:
261.1722.
4.2.25. 2-Isopropylidene-3-oxo-oct-4-enoic acid diethyl-
amide /17e). The reaction was carried out according to
typical procedure A. IR *neat): 2965 *m), 2933 *m), 2874
*w), 1675 *m), 1626 *vs), 1427 *m), 1285 *m), 1166 *m), 982
*w) cm21
.
1H NMR *CDCl3, 300 MHz): d. 13C NMR
4.2.30.
/2-Benzenesulfonyl-penta-1,4-dienyl)-benzene
*CDCl3, 75 MHz): d 190.9, 168.5, 150.8, 146.3, 135.7,
129.3, 43.1, 39.3, 34.9, 23.6, 22.0, 21.6, 14.2, 14.0, 12.8.
m/z *EI-MS): 251 *7), 236 *51), 208 *13), 182 *32), 151 *16),
100 *49), 97 *57), 83 *15), 72 *100), 67 *10), 55 *28).
HRMS: calcd for C15H25NO2 251.1885, found: 251.1886.
/21a). The reaction was carried out according to typical
procedure A. IR *neat): 3064 *w), 2920 *w), 1639 *m),
1625 *m), 1447 *m), 1304 *s), 1148 *s), 1086 *s), 920 *m),
773 *m) cm21. 1H NMR *CDCl3, 300 MHz): d 7.89 *s, 1H),
7.84 *d, Jˆ8.1 Hz, 2H), 7.53±7.30 *m, 8H), 5.61 *ddt,
Jˆ17.1, 10.5, 7. 0 Hz, 1H), 4.92±4.84 *m, 2H), 3.23 *dt,
Jˆ7.0, 1.5 Hz, 2H). 13C NMR *CDCl3, 75 MHz): d 139.7,
138.9, 133.3, 132.8, 129.8, 129.1, 128.7, 128.4, 117.3, 31.1.
m/z *EI-MS): 284 *10), 142 *100), 128 *46), 115 *33), 77
*11). HRMS: calcd for C17H16O2S 284.0871, found:
284.0846.
4.2.26. 3-Methyl-but-2-enoic acid diallylamide /17f). The
reaction was carried out according to typical procedure A.
IR *neat): 3082 *m), 2980 *m), 2914 *m), 1651 *s), 1627
*vs), 1456 *s), 1410 *s), 1235 *s), 1180 *s), 922 *s) cm21. 1H
NMR *CDCl3, 300 MHz): d 5.74 *m, 1H), 5.73±5.67 *m,
2H), 5.14±5.02 *m, 4H), 3.93 *d, Jˆ5.7 Hz, 2H), 3.82 *d,
Jˆ5.1 Hz, 2H), 1.89 *d, Jˆ1.2 Hz, 3H), 1.76 *d, Jˆ1.2 Hz,
3H). 13C NMR *CDCl3, 75 MHz): d 168.5, 148.0, 133.8,
133.4, 118.0, 117.3, 117.0, 49.9, 47.5, 26.8, 20.6. m/z
*EI-MS): 179 *8), 164 *10), 96 *10), 83 *100), 55 *19).
HRMS: calcd for C11H17NO 179.1310, found: 179.1307.
4.2.31. 4-Benzenesulfonyl-2-methylene-5-phenyl-pent-4-
enoic acid ethyl ester /21b). The reaction was carried out
according to typical procedure A; mpˆ808C. IR *neat):
3063 *w), 3032 *w), 2982 *w), 1712 *s), 1633 *m), 1447
*m), 1307 *m), 1271 *s), 1144 *s), 1089 *m), 780 *m), 748
*m), 690 *m) cm21. 1H NMR *CDCl3, 300 MHz): d 8.08 *s,
1H), 7.93±7.89 *m, 2H), 7.62±7.37 *m, 8H), 6.19 *m, 1H),
5.48 *m, 1H), 4.21 *q, Jˆ7.2 Hz, 2H), 3.57 *s, 2H), 1.30 *t,
Jˆ7.2 Hz, 3H). 13C NMR *CDCl3, 75 MHz): d 166.6, 141.4,
139.8, 138.0, 126.9, 61.5, 29.8, 14.6. m/z *EI-MS): 311 *6),
215 *100), 187 *21), 141 *22), 115 *10). Anal. calcd for
4.2.27. 2-Isopropylidene-pent-4-enoic acid diallylamide
/17g). The reaction was carried out according to typical
procedure A. IR *neat): 3080 *m), 2980 *m), 2916 *m),
1628 *s), 1450 *s), 1409 *s), 1295 *w), 1227 *m), 994 *m),
921 *s) cm21. 1H NMR *CDCl3, 300 MHz): d 5.80±5.60 *m,

J. Thibonnet et al. / Tetrahedron 58 ,2002) 4787±4799
4797
1
C20H20SO4: C, 67.39; H, 5.66; S, 9.00%. Found: C, 67.38;
H, 5.60; S, 9.30%.
*m) cm21. H NMR *CDCl3, 300 MHz): d 8.02 *s, 1H),
7.93±7.87 *m, 4H), 7.63±7.53 *m, 3H), 7.34±7.22 *m,
5H), 6.84 *d, Jˆ9.0 Hz, 2H), 3.81 *s, 3H). 13C NMR
*CDCl3, 75 MHz): d 190.6, 165.1, 141.3, 140.2, 134.0,
132.8, 131.9, 131.4, 130.7, 129.5, 129.3, 129.1, 129.0,
114.5, 55.9. m/z *EI-MS): 378 *2), 314 *70), 237 *23), 221
*19), 135 *100), 77 *16). HRMS: calcd for C22H18O4S
378.0926, found: 378.0928.
4.2.32.
/1-Benzenesulfonyl-2-phenyl-vinyl)-trimethyl-
silane /21c). The reaction was carried out according to
typical procedure A. IR *neat): 3084 *w), 3063 *w), 2958
*m), 2958 *m), 2898 *m), 1601 *w), 1582 *m), 1569 *s), 1492
*m), 1445 *m), 1296 *s), 1287 *s), 1251 *s), 1136 *s), 1084
*s), 912 *s), 849 *s), 719 *s) cm21 1H NMR *CDCl3,
.
300 MHz): d 8.38 *s, 1H), 7.91±7.88 *m, 2H), 7.60±7.49
*m, 3H), 7.38±7.22 *m, 5H), 0.0 *s, 9H). 13C NMR *CDCl3,
75 MHz): d 153.9, 145.5, 140.6, 135.0, 132.1, 128.4, 128.2,
127.5, 127.4, 126.8, 0.0. m/z *EI-MS): 301 *78), 199 *16),
183 *14), 174 *76), 167 *26), 159 *78), 145 *13), 135 *100),
125 *16), 102 *35), 97 *15), 77 *43), 73 *90), 58 *11).
HRMS: calcd for C17H20O2SiS 316.0953, found: 316.0937.
4.2.37. 5-/Hydroxy-phenyl-methyl)-2,2-dimethyl-6-
phenyl-[1,3]dioxin-4-one /26a). The reaction was carried
out according to typical procedure A. IR *neat): 3483 *m),
.
1713 *s), 1621 *m), 1371 *m) cm21 1H NMR *CDCl3,
300 MHz): d 7.53±7.17 *m, 10H), 5.52 *d, Jˆ11.5 Hz,
1H), 4.08 *d, Jˆ11.7 Hz, 1H), 1.73 *s, 3H), 1.69 *s, 3H).
13C NMR *CDCl3, 75 MHz): d 163.9, 163.1, 143.3, 132.1,
131.5, 129.4, 129.2, 128.7, 127.6, 125.9, 108.2, 106.4, 70.6,
26.6, 24.7 m/z *EI-MS): 310 *1), 252 *41), 223 *69), 207
*21), 147 *26), 105 *100), 77 *68). HRMS: calcd for
C19H18O4 310.1205, found 310.1211.
4.2.33. 2-Benzenesulfonyl-1,3-diphenyl-prop-2-en-1-ol
/21d). The reaction was carried out according to typical
procedure A. IR *neat): 3481 *s), 3056 *w), 3029 *w),
1619 *w), 1493 *m), 1446 *m), 1299 *s), 1143 *s), 1050
1
*m), 773 *m), 699 *m) cm21. H NMR *CDCl3, 300 MHz):
4.2.38. 5-/Cyclohexyl-hydroxy-methyl)-2,2-dimethyl-6-
phenyl-[1,3]dioxin-4-one /26b). The reaction was carried
out according to typical procedure A. IR *neat): 3501 *m),
d 8.06 *s, 1H), 7.41±7.29 *m, 8H), 7.21±7.15 *m, 2H),
7.04±6.93 *m, 5H), 6.01 *d, Jˆ10.2 Hz, 1H), 3.95 *d,
Jˆ10.2 Hz, 1H). 13C NMR *CDCl3, 75 MHz): d 143.7,
143.2, 141.5, 139.4, 133.1, 133.0, 130.5, 129.9, 129.3,
129.2, 128.5, 127.8, 127.7, 126.2, 69.8. m/z *EI-MS): 277
*9), 244 *50), 207 *62), 119 *60), 102 *100), 77 *89), 51 *38).
HRMS: calcd for C21H18O3S 350.0977, found: 350.0980
1
2851 *s), 1709 *s), 1621 *m), 1367 *s) cm21. H NMR
*CDCl3, 300 MHz): d 7.49±7.35 *m, 5H), 3.88 *dd, Jˆ
9.7, 11.3 Hz, 1H), 3.15 *d, Jˆ11.3 Hz, 1H), 2.08±0.42 *m,
10H), 1.79 *s, 3H), 1.70 *s, 3H). 13C NMR *CDCl3,
75 MHz): d 164.5, 163.1, 132.0, 131.9, 129.4, 128.0,
107.4, 105.9, 74.4, 43.1, 30.5, 30.4, 27.8, 26.6, 26.1, 26.0,
23.7 m/z *EI-MS): 316 *1), 233 *37), 175 *100), 105 *58), 83
*24). HRMS: calcd for C19H24O4 316.1675, found 316.1683.
4.2.34. 2-Benzenesulfonyl-1-phenyl-hexa-1,4-dien-3-ol
/21e). The reaction was carried out according to typical
procedure A; mpˆ758C. IR *neat): 3450 *vs), 3059 *w),
2916 *w), 1618 *m), 1446 *m), 1300 *s), 1146 *s), 1086
4.2.39. 5-Benzoyl-2,2-dimethyl-6-phenyl-[1,3]dioxin-4-
one /26c). The reaction was carried out according to typical
procedure A; mpˆ628C. IR *neat): 3413 *w), 2998 *w),
1
*m), 764 *m), 688 *m) cm21. H NMR *CDCl3, 300 MHz):
d 7.96 *s, 1H), 7.94±7.91 *m, 2H), 7.60±7.40 *m, 8H), 5.63
*dq, Jˆ15.1, 6.3 Hz, 1H), 5.46±5.43 *m, 1H), 5.20 *m, 1H),
3.28 *d, Jˆ8.7 Hz, 1H), 1.50 *dd, Jˆ6.3, 1.2 Hz, 3H). 13C
NMR *CDCl3, 75 MHz): d 142.9, 142.4, 141.9, 133.6,
133.1, 130.3, 130.2, 129.4, 129.1, 128.8, 128.4, 69.1, 18.0.
m/z *EI-MS): 314 *2), 244 *13), 172 *100), 157 *23), 143
*19), 129 *30), 115 *16), 102 *27), 91 *25), 77 *31), 51 *10).
HRMS: calcd for C16H18O3S 314.0977, found: 314.0952.
1
1717 *s), 1667 *m), 1362 *s), 1203 *m) cm21. H NMR
*CDCl3, 300 MHz): d 7.83±7.79 *m, 2H), 7.46±7.27 *m,
6H), 7.22±7.16 *m, 2H), 1.84 *s, 6H). 13C NMR *CDCl3,
75 MHz): d 192.1, 166.4, 160.0, 137.7, 134.0, 132.6, 131.4,
129.9, 129.0, 108.0, 107.2, 25.8. m/z *EI-MS): 223 *100),
147 *39), 105 *61), 77 *45), 51 *14). HRMS: calcd for
C19H16O4 308.1049, found 308.1062.
4.2.35. 2-Benzenesulfonyl-1,3-diphenyl-propenone /21f).
The reaction was carried out according to typical procedure
A; mpˆ1388C. IR *neat): 3063 *w), 1657 *s), 1615 *m),
1594 *m), 1577 *m), 1448 *s), 1303 *s), 1230 *s), 1144 *s),
4.2.40. 2,2-Dimethyl-6-phenyl-5-trimethylstannyl-[1,3]-
dioxin-4-one /26d). The reaction was carried out according
to typical procedure A; mpˆ1058C. IR *neat): 3436 *w),
1
2995 *m), 1692 *s), 1585 *m), 1323 *s) cm21. H NMR
1085 *m), 779 *m), 757 *m), 688 *m) cm21
.
1H NMR
*CDCl3, 300 MHz): d 7.46±7.34 *m, 5H), 1.71 *s, 6H), 0
*s, 9H). 13C NMR *CDCl3, 75 MHz): d 170.4, 165.4, 135.4,
131.5, 129.0, 128.8, 105.7, 103.3, 25.3, 26.9 m/z *EI-MS):
353 *73), 295 *100), 251 *91), 227 *43), 105 *40), 77 *31).
Anal. calcd for C15H20O3Sn: C, 49.09; H, 5.49%. Found: C,
49.31; H, 5.64%.
*CDCl3, 300 MHz): d 8.09 *s, 1H), 7.95±7.89 *m, 4H),
7.65±7.48 *m, 4H), 7.38±7.18 *m, 7H). 13C NMR *CDCl3,
75 MHz): d 191.2, 140.6, 138.8, 138.5, 134.5, 133.5, 132.7,
130.4, 130.2, 129.3, 128.8, 128.1, 127.9, 127.8, 127.6. m/z
*EI-MS): 348 *3), 284 *100), 207 *64), 191 *42), 178 *35),
129 *13), 105 *93), 77 *67), 51 *10). Anal. calcd for
C21H16O3S: C, 72.39; H, 4.63; S, 9.20%. Found: C, 72.43;
H, 4.60; S, 9.41%.
4.2.41. 2,2-Dimethyl-6-phenyl-5-phenylsulfonyl-[1,3]-
dioxin-4-one /26e). The reaction was carried out according
to typical procedure A; mpˆIR *neat): 3447 *w), 1734 *s),
1
4.2.36. 2-Benzenesulfonyl-1-/4-methoxy-phenyl)-3-phenyl-
propenone /21g). The reaction was carried out according to
typical procedure A. IR *neat): 3068 *w), 2842 *w), 1649 *s),
1613 *m), 1596 *s), 1572 *m), 1508 *w), 1448 *w), 1424 *w),
1319 *s), 1265 *s), 1241 *s), 1168 *s), 1147 *s), 823 *m), 610
1558 *m), 1338 *m) cm21. H NMR *CDCl3, 300 MHz): d
7.66±7.02 *m, 10H), 1.74 *d, Jˆ11.0 Hz, 6H). 13C NMR
*CDCl3, 75 MHz): d 170.9, 165.4, 162.2, 161.1, 136.9,
135.4, 132.3, 129.8, 129.5, 129.2, 128.5, 127.8, 126.7,
126.6, 106.6, 99.0, 91.7, 25.7. m/z *EI-MS): 312 *2), 302

4798
J. Thibonnet et al. / Tetrahedron 58 ,2002) 4787±4799
*3), 254 *10), 210 *6), 110 *18), 105 *100). HRMS: calcd for
C18H16O3S 312.0820, found 312.0828.
was added dropwise over 5 min to a solution of the
5-iodo-1,3-dioxin-4-one 24a *113 mg, 0.34 mmol) in THF
*3 mL) at 2308C under argon. The resulting solution was
then stirred for 30 min and ZnBr2 *0.41 mmol) in THF
*1.2 M, 0.34 mL) was added. The reaction mixture was
allowed to warm to room temperature to give the zinc
reagent 27a. Another dry three-necked ¯ask equipped with
an argon inlet, septum and thermometer was charged with
Pd*dba)2 *8.1 mg, 5 mol%) and tfp*6.6 mg, 10 mol%)
followed by THF *1 mL). The initial red color disappeared
after 2 min leading to a yellow solution. 4-Iodobenzonitrile
*65.2 mg, 0.28 mmol) was added followed by the zinc
reagent 27a. The reaction mixture was re¯uxed for 12 h,
worked upby pouring in aq. sat. NaCl solution and extrated
with ether. The crude residue was puri®ed by column
chromatography on silica *pentane/ether 3:1) to give 28a
*50 mg, 57%) as a white solid; mpˆ1738C. IR *neat):
4.2.42. 5-Allyl-2,2-dimethyl-6-phenyl-[1,3]dioxin-4-one
/26f). The reaction was carried out according to typical
procedure A. IR *neat): 2998 *m), 1723 *s), 1626 *m),
1
1367 *m) cm21. H NMR *CDCl3, 300 MHz): d 7.47±7.35
*m, 5H), 5.97±5.84 *m, 1H), 5.05±4.95 *m, 2H), 3.04
*td, Jˆ1.7, 5.7 Hz, 2H), 1.71 *s, 6H). 13C NMR *CDCl3,
75 MHz): d 161.7, 161.3, 135.0, 131.3, 129.8, 127.4,
124.1, 114.7, 104.3, 103.1, 29.0, 24.1. m/z *EI-MS): 244
*10), 186 *91), 158 *42), 105 *100), 77 *36). HRMS: calcd
for C15H16O3 244.1099, found 244.1105.
4.2.43. 5-/Hydroxy-phenyl-methyl)-2,2,6-trimethyl-[1,3]-
dioxin-4-one /26g). The reaction was carried out according
to typical procedure A. IR *neat): 3487 *m), 1689 *s), 1633
*m), 1398 *m) cm21. 1H NMR *CDCl3, 300 MHz): d 7.32±
7.17 *m, 5H), 5.55 *s, 1H), 4.05 *s, 1H), 2.00 *s, 3H), 1.62 *s,
3H), 1.56 *s, 3H). 13C NMR *CDCl3, 75 MHz): d 164.5,
161.1, 141.9, 127.4, 126.2, 124.3, 106.6, 104.7, 68.4, 24.5,
23.8, 16.6. m/z *EI-MS): 248 *3), 190 *75), 161 *75), 147
*100), 43 *47). HRMS: calcd for C14H16O4 248.1049, found
248.1063.
3430 *w), 1711 *s), 1616 *m), 1369 *m), 1275 *m) cm21
.
1H NMR *CDCl3, 300 MHz): d 7.47±7.10 *m, 9H), 1.83 *s,
6H). 13C NMR *CDCl3, 75 MHz): d 164.0, 161.6, 138.2,
132.4, 132.3, 131.2, 130.2, 128.8, 119.1, 111.5, 106.4,
25.6. m/z *EI-MS): 305 *3), 247 *10), 203 *14), 105 *100).
HRMS: calcd for C19H15NO3 305.3273, found 305.3290.
4.2.48.
4-/2,2,6-Trimethyl-4-oxo-4H-[1,3]dioxin-5-yl)-
benzonitrile /28b). The reaction was carried out according
to typical procedure B; mpˆ958C. IR *neat): 3428 *w), 2229
*m), 1730 *s), 1638 *s), 1397 *m), 1206 *s) cm21. 1H NMR
*CDCl3, 300 MHz): d 7.60 *d, Jˆ8.3 Hz, 2H), 7.34 *d,
Jˆ8.3 Hz, 2H), 1.90 *s, 3H), 1.71 *s, 6H). 13C NMR
*CDCl3, 75 MHz): d 166.4, 160.8, 137.9, 132.4, 131.9,
119.0, 111.9, 107.5, 106.3, 25.6, 19.2. m/z *EI-MS): 243
*11), 185 *100), 143 *79), 114 *13), 43 *74). HRMS: calcd
for C14H13NO3 243.0895, found 243.0904.
4.2.44. 5-/Cyclohexyl-hydroxy-methyl)-2,2,6-trimethyl-
[1,3]dioxin-4-one /26h). The reaction was carried out
according to typical procedure A. IR *neat): 3469 *m),
2852 *s), 1714 *s), 1634 *s), 1449 *m), 1378 *s), 1270
1
*m) cm21. H NMR *CDCl3, 300 MHz): d 3.92 *d, Jˆ
9.0 Hz, 1H), 3.36 *s, 1H), 2.15±2.05 *m, 1H), 1.95 *s,
3H), 1.80±0.7 *m, 10H), 1.60 *s, 6H). 13C NMR *CDCl3,
75 MHz): d 165.3, 162.5, 106.6, 105.6, 104.4, 74.1, 43.8,
30.4, 30.3, 26.7, 26.3, 26.1, 24.8, 17.9. m/z *EI-MS): 151
*60), 136 *20), 108 *62), 93 *71), 78 *66), 67 *100), 55 *39).
HRMS: calcd for C14H22O4 254.1518, found 254.1534.
4.2.49. 2,2-Dimethyl-5-/2-methyl-3-oxo-cyclohex-1-enyl)-
6-phenyl-[1,3]dioxin-4-one /28c). The reaction was carried
out according to typical procedure B. IR *neat): 3407 *m),
2957 *m), 1714 *s), 1603 *s), 1449 *m), 1380 *s), 1251
4.2.45. 5-Allyl-2,2,6-trimethyl-[1,3]dioxin-4-one /26i).
The reaction was carried out according to typical procedure
A. IR *neat): 3432 *w), 3000 *w), 1724 *s), 1646 *m), 1397
1
*m) cm21. H NMR *CDCl3, 300 MHz): d 7.44±7.29 *m,
1
*m) cm21. H NMR *CDCl3, 300 MHz): d 5.91±5.77 *m,
5H), 2.80±2.66 *m, 1H), 2.47±2.29 *m, 2H), 2.15±1.82 *m,
2H), 1.80 *s, 3H), 1.76 *s, 3H), 1.55 *s, 3H), 1.28±1.11 *m,
1H). 13C NMR *CDCl3, 75 MHz): d 199.3, 161.8, 160.2,
148.8, 137.1, 132.1, 129.0, 128.2, 107.4, 106.2, 38.2, 32.0,
26.1, 25.1, 23.1, 13.3. m/z *EI-MS): 253 *8), 226 *51), 198
*13), 170 *10), 105 *100), 77 *45). HRMS: calcd for
C19H20O4 312.1362, found 312.1389.
1H), 5.10±5.02 *m, 2H), 3.04 *d, Jˆ6.0 Hz, 2H), 1.99 *s,
3H), 1.68 *s, 6H). 13C NMR *CDCl3, 75 MHz): d 164.7,
162.4, 135.5, 115.5, 105.4, 103.4, 29.4, 25.5, 17.7. m/z
*EI-MS): 182 *7), 124 *60), 109 *22), 96 *28), 81 *35), 43
*100). HRMS: calcd for C10H14O3 182.0943, found
182.0925.
4.2.46.
2-/2,2,6-Trimethyl-4-oxo-4H-[1,3]dioxin-5-yl-
methyl)-acrylic acid ethyl ester /26j). The reaction was
carried out according to typical procedure A. IR *neat):
3424 *w), 2995 *m), 1722 *s), 1645 *s), 1393 *m), 1152
Acknowledgements
We thank the DFG *Leibniz program) and the Fonds der
Chemischen Industrie for ®nancial support. We thank
Chemetall GmbH *Frankfurt) and Degussa AG *Hanau)
and BASF AG for the generous gift of chemicals.
1
*m) cm21. H NMR *CDCl3, 300 MHz): d 6.16 *s, 1H),
5.54 *s, 1H), 4.26±4.17 *m, 2H), 3.21 *s, 2H), 1.94 *s,
3H), 1.58 *s, 6H), 1.21 *t, Jˆ7.1, 3H). 13C NMR *CDCl3,
75 MHz): d 167.2, 165.6, 162.1, 137.8, 126.1, 105.3, 102.6,
61.2, 27.8, 25.5, 18.0, 14.6. m/z *EI-MS): 254 *1), 197 *100),
168 *15), 151 *41), 125 *20), 99 *14). HRMS: calcd for
C13H18O5 254.1154, found 254.1163.
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