The stereoselective synthesis of alkenyl-β-lactams by palladium-catalyzed [2+2] carbonylative cycloaddition

Article abstract of DOI:10.1002/ejoc.200300667

Allyl halides of different structures, under CO pressure, in the presence of Et₃N, a catalytic amount of Pd(OAc)₂, and triphenylphosphane as ligand, undergo a [2+2] cycloaddition reaction with various imines. The reaction is highly regio- and stereoselective: β-lactams are formed in good yields and with trans diastereoselectivity in both the β-lactam ring and the vinylic moiety. New and important information is suggested regarding the known reaction mechanism. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejoc.200300667

FULL PAPER
The Stereoselective Synthesis of Alkenyl-β-lactams by Palladium-Catalyzed
[2؉2] Carbonylative Cycloaddition
[a]
[a]
[a]
[a]
Luigino Troisi,* Luisella De Vitis, Catia Granito, and Erbana Epifani
Keywords: Palladium / Cycloaddition / Alkenyl-β-lactams / Diastereoselectivity
Allyl halides of different structures, under CO pressure, in
the presence of Et N, a catalytic amount of Pd(OAc) , and
triphenylphosphane as ligand, undergo a [2+2] cycloaddition
reaction with various imines. The reaction is highly regio-
and stereoselective: β-lactams are formed in good yields and
with trans diastereoselectivity in both the β-lactam ring and
the vinylic moiety. New and important information is sug-
gested regarding the known reaction mechanism.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
3
2
Introduction
b) Palladium-catalyzed carbonylation of the aminovinyl
bromide 2. This is a convenient synthesis of vinyl β-
Among the catalyzed carbonylation reactions, the cyclo- lactams[29Ϫ31] (Scheme 2).
carbonylation catalyzed by transition metals has recently
proved to be an extremely helpful technique for the pro-
duction of interesting transformations in organic
[
1Ϫ3]
chemistry.
In particular, a large number of papers has
appeared in which palladium complexes have been used to
prepare many new and useful molecules. Particularly inter-
esting seems to be the cyclocarbonylation of unsaturated
Scheme 2
[
4Ϫ12]
alcohols,
which leads to the formation of lactones.
The analogous cyclocarbonylation of unsaturated am-
ines, leading to the formation of lactams, seems to have
[
13,14]
been studied less in the literature.
β-lactams
Of all lactams, the
c) Carbonylative coupling and cyclization reaction of the
,3 thiazines 3 with allyl phosphates, catalyzed by bis(ben-
[
15Ϫ22]
are of special biological and pharmaceut-
1
ical interest, and these compounds have also been obtained
by different synthetic pathways, summarized below:
a) Carbonylation of the aziridines 1 in the presence of a
[32]
zonitrile)palladium dichloride.
Several rhodium com-
plexes are also effective catalysts for this process
Scheme 3).
(
[23Ϫ28]
catalytic amount of [Rh(CO) Cl] .
The carbonyl in-
2
2
sertion is regio- and stereospecific, occurring at the most
substituted carbon-nitrogen bond in the aziridine ring, and
proceeding with retention of stereochemistry of the sub-
stituents linked to the aziridinic carbon atoms (Scheme 1).
Scheme 3
Scheme 1
d) Palladium-catalyzed carbonylation of the allyl phos-
phate 4 in the presence of imines, under CO pressure.[
33,34]
The reaction is stereoselective since the formation of the
Tecnologie Biologiche ed trans-7 or the cis-8 β-lactam depends on the imine used for
the coupling. An imine conjugated 6 with a carbonyl group
[
a]
Dipartimento di Scienze
e
Ambientali, University of Lecce,
Via Prov. le Lecce-Monteroni, 73100 Lecce, Italy
Fax: (internat.) ϩ39-0832-298701
E-mail: luigino.troisi@unile.it
gives the cis-β-lactam, whereas the unconjugated imine 5
gives the trans isomer (Scheme 4).
Eur. J. Org. Chem. 2004, 1357Ϫ1362
DOI: 10.1002/ejoc.200300667
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1357

L. Troisi, L. De Vitis, C. Granito, E. Epifani
FULL PAPER
[2ϩ2] Cycloaddition reactions of allyl halides of different
structures 10aϪl with the simple imines 9aϪd, under CO
pressure, in the presence of Et N, triphenylphosphane and
3
a catalytic amount of Pd(OAc) , led to β-lactams in good
2
yields and with high diastereoselectivity (Table 1). Slightly
different reaction conditions to those reported in the litera-
ture, such as the use of Et N instead of iPr NEt, allyl hal-
3
2
ides as substrates instead of the less easily accessible allyl
phosphates, and a lower pressure of CO, make this method-
ology much simpler than those reported in the literature.
The trans relative configuration was found to predominate
both in the β-lactam ring and in the CϪC double bond of
the products. The stereochemistry of the CϪC double bond
Scheme 4
3
in the products was assigned on the basis of the J
coup-
H,H
ling constants across the double bond. For the β-lactam
moiety itself, the stereochemistry was assigned based on of
No reaction products, or just traces of β-lactams, were the coupling constants between the protons linked to C-3
[
33Ϫ37]
reportedly formed when allyl bromide,
allylacet- and C-4, according to the literature report that for small
ate,[
38,39]
allyl phenyl ether,
[40]
allyl carbonate[41,42] rings, Jcis Ͼ Jtrans
were used under similar reaction con- 11o,11oЈ showed trans-type coupling constants JH,H for the
[44]
.
The diastereoisomers 11n,11nЈ and
[
43]
or allylsulfone
ditions. In contrast with these observations, we found that β-lactam ring, similar to those measured for the other com-
simple allyl halides of various structures react with imines pounds. The protons of the R substituent on the nitrogen
under slightly different reaction conditions, leading to β- atom showed a difference in chemical shift (δ) between com-
lactams in a stereoselective way.
pounds 11n and 11nЈ, and between 11o and 11oЈ. This sug-
gests two possible configurations of the β-lactamic nitrogen.
According to the mechanism proposed by Torii[
(Scheme 6), the reaction starts by the formation of the π-
allyl palladium complex 16. In the acyl complex 17, derived
33]
Results and Discussion
Several imines 9aϪd, which were to be used as substrates from the insertion of CO, the protons alpha to the carbonyl
(
Scheme 5), were prepared as reported in the Exp. Sect. group show appreciable acidity.
Table 1. Cyclocarbonylation of imines 9aϪd with allyl halides 10aϪg
Entry
Imine
Halide
Products (yield, %)[a]
1
2
3
4
5
6
7
8
9
9a
9a
9a
9a
9a
9a
9b
9b
9b
9b
9b
9b
9c
9d
10a
10b
10c
10d
10f
10g
10a
10c
10d
10e
10f
10g
10a
10a
11a (84)
11a (81)
11b (81)
11c (58)[
12a (5)
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
12a (6)
12b (15)
12c (traces)
Ϫ
Ϫ
Ϫ
Ϫ
13c (21)
13d (15)
14c (traces)
Ϫ
14e (14)
Ϫ
b]
[b]
11d (50)
13e (6)[
b]
[b]
Ϫ
11f (85)
11g (78)
11h (60)[
11i (98)[
Ϫ
Ϫ
Ϫ
b]
[b]
12h (traces)
13h (20)
Ϫ
13l (15)
13m (4)[
Ϫ
14h (traces)
Ϫ
Ϫ
14m (11)
Ϫ
Ϫ
10
11
12
13
14
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
b]
[b]
11l (50)
Ϫ
b]
[b]
11n (60) ϩ 11nЈ (32)
11o (53) ϩ 11oЈ (40)
Ϫ
[
a]
Isolated yields. [b] Inseparable mixture of diastereoisomers (ratio measured by GC and H NMR spectroscopy).
1
1358
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1357Ϫ1362

Stereoselective Synthesis of Alkenyl-β-lactams
FULL PAPER
Consequently, deprotonation by Et N could lead to the
3
[
45]
formation of a carbanion, or even a ketene,
which,
through an addition reaction with the imine, could form a
four-membered ring 18.
According to previously reported data,
[
33,34]
as well as
the data in Table 1, the CO insertion would always occur
between the carbon (C-3) directly attached to the halogen
and the palladium (structure 17). When the halogen is not
in the terminal position of the allylic chain, we found, in-
stead, that the insertion occurs at the less hindered carbon
atom (C-1) of structure 15. In particular, when the halo-
substrate is 3-chloro-1-butene (10h) or 3-bromo-1-butene
2
3
1
(
[
10i) (R ϭ R ϭ H, R ϭ CH ), or 3-bromo-1-hexene (10l)
3
2
3
1
R ϭ R ϭ H, R ϭ (CH ) CH ], carbonylation occurs at
2 2 3
the C-1 position, and not at C-3 (Table 2).
In fact, in these cases, we isolated the same reaction prod-
ucts as were obtained when crotyl bromide (10d) or 1-
bromo-2-hexene (10f) were used to form the intermediate
π-allyl palladium complex (Entries 4, 5, 9 and 11, Table 1).
The low yield obtained with 3-bromocyclohexene (10g)
(Entries 6 and 12, Table 1) could be caused by steric effects.
The formation of the π-allyl palladium complex, and the
subsequent terminal double-bond shift, could not proceed
easily for steric reasons, resulting in a considerably lower
yield for this reaction.
Scheme 5
Conclusion
This protocol can be used to synthesize a large number
of new alkenyl-β-lactams stereoselectively. The main advan-
tages of our method, compared to those reported in the
literature, are that Et N may be used as base, and that sim-
3
ple allyl halides may be used as substrates instead of the
less easily accessible allyl phosphates.
Scheme 6
Table 2. Cyclocarbonylation of imines 9aϪb with allyl halides 10hϪl
Entry
Imine
Halide
Products (yield, %)[a]
1
2
3
4
5
6
9a
9b
9a
9b
9a
9b
10h
10h
10i
10i
10l
10l
11c (60)
11h (60)[
11c (55)
11h (65)[
12c (traces)
12h (traces)
12c (traces)
12h (traces)
Ϫ
13c (20)
13h (25)
13c (23)
13h (23)
13d (14)
14c (traces)
14h (traces)
14c (traces)
14h (traces)
Ϫ
b]
[b]
b]
b]
[b]
[b]
[
11d (52)
11l (53)[
b]
Ϫ
13l (15)
[b]
Ϫ
[
a]
Isolated yields. [b] Inseparable mixture of diastereoisomers (ratio measured by GC and H NMR spectroscopy).
1
Eur. J. Org. Chem. 2004, 1357Ϫ1362
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1359

L. Troisi, L. De Vitis, C. Granito, E. Epifani
FULL PAPER
Moreover, we have shown a new aspect of the suggested (100.62 MHz, CDCl
3
): δ ϭ 58.4, 58.8, 117.2, 120.9, 123.9, 127.0,
1
28.3, 128.7, 128.8, 129.0, 134.7, 137.5, 165.4 ppm. GC-MS
mechanism: the CO insertion can occur on either of the
carbon atoms of the intermediate π-allyl palladium com-
plex, depending on the steric environment.
ϩ
(
(
1
70 eV): m/z (%) ϭ 249 (5) [M ], 181 (30), 180 (33), 130 (100), 129
64), 115 (26), 77 (50). IR (film): ν˜ ϭ 3050 cm , 3020, 3000, 2910,
740, 1600, 1370. (From allylic halide 10b) trans-11a: Yield 202 mg
Ϫ1
(
81%), cis-12a: 15 mg (6%).
Experimental Section
3-(2-Methylpropenyl)-1,4-diphenylazetidin-2-one, (trans-11b): Yield
1
224 mg (81%), solid. M.p. 101.0Ϫ103.0 °C (n-hexane). H NMR
General Remarks: THF, allyl bromide, allyl chloride, crotyl bro-
mide, 1-chloro-3-methyl-2-butene, cinnamyl chloride, 3-bromo-
cyclohexene, 3-chloro-1-butene, (ϩ/Ϫ)-α-methylbenzylamine, ani-
line, benzaldehyde, triethylamine, palladium() acetate, tri-
(400.13 MHz, CDCl ): δ ϭ 1.60 (s, 3 H), 1.79 (s, 3 H), 3.88 (dd,
3
J ϭ 7.8, 2.4 Hz, 1 H), 4.70 (d, J ϭ 2.4 Hz, 1 H), 5.40 (d, J ϭ
7.6 Hz, 1 H), 7.05 (t, J ϭ 7.2 Hz, 1 H), 7.20Ϫ7.37 (m, 9 H) ppm.
1
3
3
C NMR (100.62 MHz, CDCl ): δ ϭ 18.7, 25.7, 60.3, 62.3, 116.9,
phenylphosphane and all other chemicals were of commercial grade 117.1, 123.7, 125.8, 128.3, 128.9, 129.1, 137.7, 137.8, 139.1,
ϩ
(
Aldrich), and they were used without further purification. Imines
166.9 ppm. GC-MS (70 eV): m/z (%) ϭ 277 (1) [M ], 180 (17), 158
): ν˜ ϭ 3030
19NO (277.37): calcd. C
prepared starting from commercially available 1-butene, 2-hexene 82.28, H 6.90, N 5.05; found C 82.38, H 7.08, N 5.01. cis-(12b):
were prepared starting from the corresponding carbonyl com- (72), 143 (100), 128 (20), 115 (10), 77 (32). IR (CHCl
3
[
46]
Ϫ1
pounds and amines.
The allylic halides 10f, 10i and 10l were
cm , 2970, 2910, 1740, 1600, 1370. C19H
1
and 1-hexene, respectively, by bromination with N-bromosuccinim-
3
Yield 42 mg (15%), oil. H NMR (400.13 MHz, CDCl ): δ ϭ 1.53
ide. Petroleum ether refers to the fraction boiling in the range
(s, 3 H), 1.66 (s, 3 H), 4.48 (dd, J ϭ 9.0, 6.0 Hz, 1 H), 4.76 (d, J ϭ
1
13
4
0Ϫ60 °C. H and C NMR spectra were recorded with a Bruker
9.0 Hz, 1 H), 5.25 (d, J ϭ 6.0 Hz, 1 H), 7.04 (t, J ϭ 7.3 Hz, 1 H),
1
13
Avance 400 spectrometer (400.13 MHz and 100.62 MHz, for
and C, respectively), with CDCl
H
3
7.20Ϫ7.36 (m, 9 H) ppm. C NMR (100.62 MHz, CDCl ): δ ϭ
1
3
3
as the solvent (δ ϭ 7.24 ppm
22.7, 29.7, 54.3, 59.3, 114.6, 117.2, 123.7, 127.0, 128.0, 128.6, 129.0,
for 1H spectra; δ ϭ 77.0 ppm for C spectra) with TMS as an
internal standard. IR spectra were recorded with a PerkinϪElmer
spectrometer Model 283. GC-MS analyses were performed with a
ShimadzuϪ17A gas chromatograph (5% diphenyl/95% dimethylpo-
lysiloxane capillary column, 30 m, 0.25 mm i.d.), equipped with a
Shimadzu GCMSϪQP5050A mass-selective detector operating at
13
135.3, 137.7, 139.1, 167.1 ppm. GC-MS (70 eV): m/z (%) ϭ 277 (1)
ϩ
[M ], 180 (17), 158 (72), 143 (100), 128 (20), 115 (10), 77 (32). IR
Ϫ1
(film): ν˜ ϭ 3030 cm , 2970, 2910, 1740, 1600, 1370.
1,4-Diphenyl-3-propenylazetidin-2-one (trans,trans-11c): (From al-
lylic halide 10d). Yield 153 mg (58%), solid. M.p. 74.0Ϫ76.0 °C (n-
1
hexane). H NMR (400.13 MHz, CDCl
3
): δ ϭ 1.74 (d, J ϭ 6.0 Hz,
H), 3.66 (dd, J ϭ 8.1, 2.3 Hz, 1 H), 4.74 (d, J ϭ 2.3 Hz, 1 H),
.62Ϫ5.84 (m, 2 H), 7.01 (t, J ϭ 7.5 Hz, 1 H), 7.19Ϫ7.50 (m, 9 H)
70 eV (EI). Microanalyses were performed on a CarloϪErba
3
5
C,H,N analyser. Melting points were determined using an electro-
thermal melting point apparatus and are uncorrected. TLC was
performed on Merck silica gel plates with F-254 indicator; viewing
was by UV light (254 nm). Column chromatography was performed
on silica gel (63Ϫ200 mm) using petroleum ether/diethyl ether
1
3
ppm. C NMR (100.62 MHz, CDCl
3
): δ ϭ 18.0, 61.6, 63.4, 116.8,
1
1
23.3, 123.7, 125.6, 128.4, 128.9, 129.0, 130.4, 131.2, 137.4,
ϩ
66.0 ppm. GC-MS (70 eV): m/z (%) ϭ 263 (4) [M ], 181 (35), 180
):
17NO (263.34):
(
55), 144 (89), 129 (100), 128 (62), 115 (25), 77 (83). IR (CHCl
3
2
(Et O) mixtures as eluents. All reactions involving air-sensitive re-
Ϫ1
ν˜ ϭ 3020 cm , 2920, 1740, 1600, 1490, 1370. C18
H
agents were performed under nitrogen in oven-dried glassware,
using syringe/septum cap techniques.
calcd. C 82.10, H 6.51, N 5.32; found C 81.86, H 6.42, N 5.15.
1
trans,cis-13c: Yield 55 mg (15%), oil. H NMR (400.13 MHz,
General Procedure for the Preparation of β-Lactams: 9aϪd
CDCl
3
): δ ϭ 1.59 (dd, J ϭ 6.8, 1.1 Hz, 3 H), 3.99 (dd, J ϭ 9.0,
(
(
1.0 mmol), 10aϪl (1.5 mmol), PPh
3 2
(0.08 mmol), Pd(AcO)
2.3 Hz, 1 H), 4.74 (d, J ϭ 2.3 Hz, 1 H), 5.62Ϫ5.84 (m, 2 H), 7.01
1
3
0.02 mmol), and Et N (2 mmol) were dissolved in THF (10 mL),
3
(t, J ϭ 7.5 Hz, 1 H), 7.19Ϫ7.50 (m, 9 H) ppm. C NMR
(100.62 MHz, CDCl ): δ ϭ 13.7, 58.9, 61.8, 116.8, 122.5, 123.7,
and placed in a 45 mL autoclave. The autoclave was purged, pressu-
rized (400 psi of CO), and then heated to 100 °C for 18 h. The
reaction mixture was then cooled to room temperature, and worked
up by the addition of water (5 mL) and extraction with Et
ϫ 5 mL). The combined organic layers were dried (Na SO
concentrated in vacuo. The crude products were purified by column
3
125.7, 128.3, 128.8, 129.0, 130.4, 131.3, 137.5, 166.0 ppm. GC-MS
ϩ
(70 eV): m/z (%) ϭ 263 (2) [M ], 180 (18), 144 (64), 129 (100), 115
Ϫ1
O (3 (10), 77 (34). IR (film): ν˜ ϭ 3060 cm , 3020, 2920, 1740, 1600,
2
2
4
) and
1490, 1370. (From allylic halides 10h and 10i) Yield trans,trans-11c:
158 mg (60%) and 144 mg (55%), trans,cis-13c: 66 mg (25%) and
60 mg (23%) respectively.
2
chromatography (silica gel, petroleum ether/Et O, 7:3) to afford the
pure β-lactams; yields: 15Ϫ98%.
3-(Pent-1-enyl)-1,4-diphenylazetidin-2-one (inseparable mixture of
1
1
,4-Diphenyl-3-vinylazetidin-2-one (trans-11a): From allylic halide
diastereoisomers, 50:15): (from allylic halide 10f). Overall yield
1
1
0a, yield 209 mg (84%), solid. M.p. 97.2Ϫ99.2 °C (n-hexane). H
): δ ϭ 3.74 (dd, J ϭ 7.8, 2.4 Hz, 1 H), CDCl
.81 (d, J ϭ 2.4 Hz, 1 H), 5.35 (dd, J ϭ 23.9, 17.2 Hz, 2 H), H), 2.06 (q, J ϭ 7.4 Hz, 2 H), 3.67 (dd, J ϭ 8.0, 2.2 Hz, 1 H), 4.74
.00Ϫ6.10 (m, 1 H), 7.05 (t, J ϭ 7.2 Hz, 1 H), 7.16Ϫ7.40 (m, 9 H) (d, J ϭ 2.2 Hz, 1 H), 5.63 (dd, J ϭ 8.0, 15.2 Hz, 1 H), 5.73Ϫ5.80
190 mg (65%), oil. trans,trans-11d:
H NMR (400.13 MHz,
NMR (400.13 MHz, CDCl
4
6
3
3
): δ ϭ 0.91 (t, J ϭ 7.4 Hz, 3 H), 1.41 (sext, J ϭ 7.4 Hz, 2
13
13
ppm. C NMR (100.62 MHz, CDCl
3
): δ ϭ 61.2, 64.0, 117.0, 119.9,
(m, 1 H), 7.02 (t, J ϭ 7.2 Hz, 1 H), 7.20Ϫ7.38 (m, 9 H) ppm.
C
1
23.9, 125.8, 128.6, 129.1, 129.2, 130.5, 137.3, 138.1, 165.3 ppm. NMR (100.62 MHz, CDCl
3
): δ ϭ 13.6, 22.1, 34.6, 61.9, 63.5, 117.0,
ϩ
GC-MS (70 eV): m/z (%) ϭ 249 (5) [M ], 181 (30), 180 (33), 130 122.3, 123.8, 125.8, 128.4, 128.5, 129.0, 129.1, 136.5, 137.6,
Ϫ1
ϩ
(100), 129 (64), 115 (26), 77 (50). IR (CHCl
3
): ν˜ ϭ 3050 cm
,
166.2 ppm. GC-MS (70 eV): m/z (%) ϭ 291 (2) [M ], 181(15), (180
1
3
8
1
020, 3000, 2910, 1740, 1600, 1370. C17
H15NO (249.31): calcd. C
(22), 172 (100), 77 (50). trans,cis-13d: H NMR (400.13 MHz,
1.90, H 6.06, N 5.62; found C 82.10, H 6.10, N 5.55. cis-12a: Yield CDCl
2 mg (5%), oil. 1H NMR (400.13 MHz, CDCl
): δ ϭ 4.29 (dd, H), 1.96 (q, J ϭ 7.4 Hz, 2 H), 3.97 (dd, J ϭ 8.0, 2.2 Hz, 1 H), 4.72
(d, J ϭ 2.2 Hz, 1 H), 5.63 (dd, J ϭ 8.0, 8.0 Hz, 1 H), 5.73Ϫ5.80
3
): δ ϭ 0.83 (t, J ϭ 7.4 Hz, 3 H), 1.33 (sext, J ϭ 7.4 Hz, 2
3
J ϭ 6.5, 6.4 Hz, 1 H), 5.08Ϫ5.12 (m, 1 H), 5.25Ϫ5.39 (m, 3 H),
7
.06 (t, J ϭ 7.3 Hz, 1 H), 7.16Ϫ7.34 (m, 9 H) ppm. 13C NMR (m, 1 H), 7.02 (t, J ϭ 7.2 Hz, 1 H), 7.20Ϫ7.38 (m, 9 H) ppm. 13
C
1360
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1357Ϫ1362

Stereoselective Synthesis of Alkenyl-β-lactams
NMR (100.62 MHz, CDCl ): δ ϭ 13.6, 22.6, 29.7, 59.4, 62.1, 116.9,
FULL PAPER
(85%), trans,trans-11h and trans,cis-13h in a ratio 65:25; (from
3
1
1
21.8, 125.8, 127.3, 127.4, 128.6, 129.0, 129.2, 136.3, 137.7, allylic halide 10i) overall yield 244 mg (88%), trans,trans-11h and
ϩ
66.2 ppm. GC-MS (70 eV): m/z (%) ϭ 291 (2) [M ], 181 (15), 180
trans,cis-13h in a ratio 65:25.
(
22), 172 (100), 77 (50). IR (film) measured on the mixture: ν˜ ϭ
Ϫ1
trans,trans-1-Benzyl-4-phenyl-3-styrylazetidin-2-one (11i): Yield
3060 cm , 3000, 2910, 1740, 1595, 1490, 1370. (From allylic halide
1
332 mg (98%), oil. H NMR (400.13 MHz, CDCl
3
): δ ϭ 3.83 (d,
10l) Overall yield 192 mg (66%), trans,trans-11d and trans,cis-13d
J ϭ 15.0 Hz, 1 H), 3.83Ϫ3.86 (m, 1 H), 4.27 (d, J ϭ 2.1 Hz, 1 H),
.90 (d, J ϭ 15.0 Hz, 1 H), 6.26 (dd, J ϭ 15.8, 8.4 Hz, 1 H), 6.58
in a ratio 52:14.
4
1
3
2
,3-Diphenyl-2-azaspiro[3,5]non-5-en-1-one (inseparable mixture of
(d, J ϭ 15.8 Hz, 1 H), 7.20Ϫ7.40 (m, 15 H) ppm. C NMR
(100.62 MHz, CDCl ): δ ϭ 44.6, 61.3, 63.7, 122.1, 126.4, 126.5,
3
): δ ϭ 1.50Ϫ2.20 (m, 6 H), 4.92 (s, 127.7, 127.8, 128.4, 128.5, 128.6, 128.8, 129.1, 134.1, 135.4, 136.4,
diastereoisomers, 6:14): Overall yield 57 mg (20%), oil. trans-13e:
3
1
H NMR (400.13 MHz, CDCl
H), 5.83 (d, J ϭ 10.0 Hz, 1 H), 6.06 (dt, J ϭ 10.0, 6.0 Hz, 1 H);
.15Ϫ7.35 (m, 10 H) ppm. 13C NMR (100.62 MHz, CDCl
): δ ϭ (30), 194 (28), 144 (27), 115 (35), 91 (100). IR (film): ν˜ ϭ 3060
9.6, 25.1, 29.7, 58.8, 67.0, 117.3, 126.6, 127.6, 128.0, 128.6, 128.7, cm , 3020, 2900, 1750, 1600, 1590, 1450, 1350, 730, 690.
28.9, 129.7, 130.1, 134.5, 170.2 ppm. GC-MS (70 eV): m/z (%) ϭ
ϩ
1
7
1
1
2
137.1, 168.1 ppm. GC-MS (70 eV): m/z (%) ϭ 339 (0) [M ], 195
3
Ϫ1
ϩ
1
1-Benzyl-3-(pent-1-enyl)-4-phenylazetidin-2-one (inseparable mixture
of diastereoisomers, 50:15): (From allylic halide 10f). Overall yield
89 (2) [M ], 180 (22), 170 (100), 155 (17). trans-14e: H NMR
): δ ϭ 1.50Ϫ2.20 (m, 6 H), 4.88 (s, 1 H), 5.19
d, J ϭ 10.0 Hz, 1 H), 5.77 (dt, J ϭ 10.0, 6.0 Hz, 1 H), 7.15Ϫ7.35
(
(
(
400.13 MHz, CDCl
3
2
29 mg (75%), mixture of solid. M.p. 60Ϫ63 °C (n-hexane).
1
m, 10 H) ppm. 1 C NMR (100.62 MHz, CDCl
3
trans,trans-11l: H NMR (400.13 MHz, CDCl
3
): δ ϭ 0.87 (t, J ϭ
3
): δ ϭ 19.9, 24.6,
0.6, 60.4, 67.8, 117.3, 122.1, 123.7, 126.6, 127.9, 128.7, 129.0,
33.0, 135.5, 137.8, 170.2 ppm. GC-MS (70 eV): m/z (%) ϭ 289 (2)
7.3 Hz, 3 H), 1.37 (sext, J ϭ 7.3 Hz, 2 H), 2.00 (q, J ϭ 7.3 Hz, 2
3
1
H), 3.61 (dd, J ϭ 8.0, 1.6 Hz, 1 H), 3.76 (d, J ϭ 15.0 Hz, 1 H),
4.14 (d, J ϭ 1.6 Hz, 1 H), 4.86 (d, J ϭ 15.0 Hz, 1 H), 5.50 (dd,
J ϭ 16.0, 8.0 Hz, 1 H), 5.66Ϫ5.70 (m, 1 H), 7.13 (d, J ϭ 6.5 Hz, 2
ϩ
[
M ], 180 (22), 170 (100), 155 (17). IR (film) measured on the mix-
ture: ν˜ ϭ 3050 cm , 3000, 2905, 1735, 1595, 1490, 1370.
Ϫ1
1
3
H), 7.22 (d, J ϭ 6.5 Hz, 2 H), 7.27Ϫ7.37 (m, 6 H) ppm. C NMR
(100.62 MHz, CDCl ): δ ϭ 13.5, 22.0, 34.5, 44.3, 61.2, 63.4, 122.5,
trans-1-Benzyl-4-phenyl-3-vinylazetidin-2-one (11f): Yield 223 mg
3
1
(
85%), oil. H NMR (400.13 MHz, CDCl
3
): δ ϭ 3.64 (dd, J ϭ 7.7, 126.3, 127.5, 128.26, 128.3, 128.31, 128.6, 128.8, 135.6, 137.3,
ϩ
1
4
5
.8 Hz, 1 H), 3.76 (d, J ϭ 15.0 Hz, 1 H), 4.19 (d, J ϭ 1.8 Hz, 1 H),
.83 (d, J ϭ 15.0 Hz, 1 H), 5.23 (dd, J ϭ 23.0, 17.1 Hz, 2 H), (62), 143 (45), 129 (100), 115 (17), 91 (59). trans,cis-13l: H NMR
.86Ϫ5.94 (m, 1 H), 7.11 (d, J ϭ 6.5 Hz, 1 H), 7.15Ϫ7.35 (m, 9 H) (400.13 MHz, CDCl ): δ ϭ 0.77 (t, J ϭ 7.3 Hz, 3 H), 1.33 (sext,
168.7 ppm. GC-MS (70 eV): m/z (%) ϭ 305 (1) [M ], 196 (10), 172
1
3
13
ppm. C NMR (100.62 MHz, CDCl
3
): δ ϭ 44.1, 60.3, 63.6, 118.7,
J ϭ 7.3 Hz, 2 H), 1.90 (q, J ϭ 7.3 Hz, 2 H), 3.77 (d, J ϭ 15.0 Hz,
1 H),3.90 (dd, J ϭ 8.0, 1.6 Hz, 1 H), 4.14 (d, J ϭ 1.6 Hz, 1 H),
1
1
26.1, 127.3, 128.0, 128.2, 128.4, 128.7, 130.6, 135.1, 136.8,
ϩ
67.5 ppm. GC-MS (70 eV): m/z (%) ϭ 263 (1) [M ], 194 (5), 130 4.84 (d, J ϭ 15.0 Hz, 1 H), 5.50 (dd, J ϭ 8.0, 8.0 Hz, 1 H),
Ϫ1
(
100), 129 (90), 115 (55), 91 (75). IR (film): ν˜ ϭ 3060 cm , 3020, 5.66Ϫ5.70 (m, 1 H), 7.13 (d, J ϭ 6.5 Hz, 2 H), 7.22 (d, J ϭ 6.5 Hz,
1
3
2900, 1740, 1490, 1390.
2 H), 7.27Ϫ7.37 (m, 6 H) ppm. C NMR (100.62 MHz, CDCl
δ ϭ 13.5, 22.4, 29.8, 44.4, 59.3, 61.4, 122.0, 126.3, 127.5, 128.2,
28.3, 128.4, 128.6, 128.9, 135.5, 137.3, 168.7 ppm. GC-MS
3
):
trans-1-Benzyl-3-(2-methylpropenyl)-4-phenylazetidin-2-one (11g):
1
1
Yield 227 mg (78%), oil. H NMR (400.13 MHz, CDCl
(
(
3
): δ ϭ 1.51
d, J ϭ 1.0 Hz, 3 H), 1.72 (s, 3 H), 3.76 (d, J ϭ 15.0 Hz, 1 H), 3.83
dd, J ϭ 7.9, 2.1 Hz, 1 H), 4.10 (d, J ϭ 2.1 Hz, 1 H), 4.83 (d, J ϭ
5.0 Hz, 1 H), 5.30 (dq, J ϭ 7.9, 1.0 Hz, 1 H), 7.11Ϫ7.37 (m, 10
ϩ
(
(
70 eV): m/z (%) ϭ 305 (1) [M ], 196 (10), 172 (62), 143 (45), 129
100), 115 (17), 91 (59). IR (film) measured on the mixture: ν˜ ϭ
060 cm , 3000, 2910, 1740, 1600, 1490, 1380, 1110. C21H23NO
Ϫ1
3
1
(
305.42) measured on the mixture: calcd. C 82.58, H 7.59, N 4.59;
13
H) ppm. C NMR (100.62 MHz, CDCl
3
): δ ϭ 18.3, 25.3, 44.1,
found C 82.10, H 7.72, N 4.50. (From allylic halide 10l). Overall
yield 207 mg (68%), trans,trans-11l and trans,cis-13l in a ratio
5
1
1
1
9.9, 61.3, 117.1, 126.0, 126.1, 127.3, 128.0, 128.4, 128.6, 135.3,
ϩ
37.2, 137.8, 169.0 ppm. GC-MS (70 eV): m/z (%) ϭ 291 (0) [M ],
53:15.
Ϫ1
95 (30), 194 (30), 91 (100). IR (film): ν˜ ϭ 3060 cm , 3030, 2920,
740, 1600, 1500, 1390.
2-Benzyl-3-phenyl-2-azaspiro[3.5]non-5-en-1-one (inseparable mix-
ture of diastereoisomers, 4:11): Overall yield 45 mg (15%), oil. trans-
1
-Benzyl-4-phenyl-3-propenylazetidin-2-one (inseparable mixture of
1
13m: H NMR (400.13 MHz, CDCl
3
): δ ϭ 1.50Ϫ2.10 (m, 6 H),
diastereoisomers, 60:20): (From allylic halide 10d). Overall yield
3.90 (d, J ϭ 14.8 Hz, 1 H), 4.28 (s, 1 H), 4.96 (d, J ϭ 14.8 Hz, 1
1
2
22 mg (80%), oil. trans,trans-11h:
CDCl ): δ ϭ 1.70 (d, J ϭ 6.4 Hz, 3 H), 3.60 (dd, J ϭ 8.0, 2.0 Hz,
H), 3.77 (d, J ϭ 15.0 Hz, 1 H), 4.14 (d, J ϭ 2.0 Hz, 1 H), 4.85
d, J ϭ 15.0 Hz, 1 H), 5.53 (dd, J ϭ 16.8, 8.0 Hz, 1 H), 5.70 (dq,
J ϭ 16.8, 6.4 Hz, 1 H), 7.13Ϫ7.37 (m, 10 H) ppm. trans,cis-13h:
H NMR (400.13 MHz,
H), 5.67 (d, J ϭ 10.2 Hz, 1 H), 5.96 (dt, J ϭ 10.2, 6.3 Hz, 1 H),
3
1
7
.15Ϫ7.39 (m, 10 H). cis-14m: H NMR (400.13 MHz, CDCl
δ ϭ 1.5 0Ϫ2.10 (m, 6 H), 3.88 (d, J ϭ 14.8 Hz, 1 H), 4.22 (s, 1 H),
.00 (d, J ϭ 14.8 Hz, 1 H), 5.23 (d, J ϭ 10.2 Hz, 1 H), 5.71 (dt,
3
):
1
(
5
13
J ϭ 10.2, 6.3 Hz, 1 H), 7.15Ϫ7.39 (m, 10 H) ppm. C NMR,
GC-MS and IR data were measured on the mixture. C NMR
1
H NMR (400.13 MHz, CDCl
.77 (d, J ϭ 15.0 Hz, 1 H), 3.93 (dd, J ϭ 8.0, 2.0 Hz, 1 H), 4.12
d, J ϭ 2.0 Hz, 1 H), 4.85 (d, J ϭ 15.0 Hz, 1 H), 5.53 (dd, J ϭ 8.0,
.0 Hz, 1 H), 5.70 (dq, J ϭ 8.0, 6.8 Hz, 1 H), 7.13Ϫ7.37 (m, 10 H)
3
): δ ϭ 1.55 (d, J ϭ 6.8 Hz, 3 H),
13
3
(
8
(
100.62 MHz, CDCl
3
): δ ϭ 19.1, 19.9, 24.4, 24.6, 24.7, 30.0, 44.1,
4
1
1
4.3, 60.9, 61.2, 65.8, 67.3, 122.4, 125.7, 126.9, 127.2, 127.6, 127.7,
27.8, 128.1, 128.3, 128.4, 128.5, 128.6, 128.7, 128.8, 132.1, 132.5,
13
ppm. C NMR, GC-MS and IR data were measured on the mix-
ture. 13C NMR (100.62 MHz, CDCl
): δ ϭ 13.6, 17.9, 44.3, 44.4,
8.9, 61.1, 61.3, 63.5, 121.7, 122.8, 123.7, 126.38, 126.4, 127.4,
35.6, 135.8, 136.0, 138.1, 172.6, 172.8 ppm. GC-MS (70 eV): m/z
3
ϩ
(%) ϭ 303 (2) [M ], 196 (7), 170 (100), 155 (17), 144 (17), 142 (17),
5
1
1
Ϫ1
1
3
41 (16), 115 (10), 108 (22), 91 (67). IR (film): ν˜ ϭ 3060 cm
,
020, 2900, 1740, 1490, 1450.
27.6, 128.3, 128.4, 128.41, 128.7, 128.9, 128.91, 129.8, 130.7,
35.4, 135.5, 137.2, 137.3, 138.0, 168.8, 168.9 ppm. GC-MS
ϩ
(
(
70 eV): m/z (%) ϭ 277 (0) [M ], 196 (7), 144 (68), 129 (100), 91
4-Phenyl-1-(1-phenyl-ethyl)-3-vinylazetidin-2-one (trans-11n): Yield
Ϫ1
1
43), 65 (20). IR (film): ν˜ ϭ 3060 cm , 3000, 2910, 1740, 1600, 166 mg (60%), oil. H NMR (400.13 MHz, CDCl
): δ ϭ 1.80 (d,
3
1490, 1380, 1100. (From allylic halide 10h) Overall yield 235 mg J ϭ 7.1 Hz, 3 H), 3.59 (dd, J ϭ 7.7, 1.9 Hz, 1 H), 4.13 (d, J ϭ
Eur. J. Org. Chem. 2004, 1357Ϫ1362
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1361

L. Troisi, L. De Vitis, C. Granito, E. Epifani
FULL PAPER
[
[
8]
9]
1
2
.9 Hz, 1 H), 4.28 (q, J ϭ 7.1 Hz, 1 H), 5.24 (dd, J ϭ 17.7, 10.3 Hz,
H. Alper, N. Hamel, J. Chem. Soc., Chem. Commun. 1990,
135Ϫ136.
E. Yoneda, T. Kaneko, S. W. Zhang, K. Onitsuka, S. Takah-
ashi, Organic Lett. 2000, 2, 441Ϫ443.
1
3
H), 5.87Ϫ5.96 (m, 1 H), 7.16Ϫ7.32 (m, 10 H) ppm. C NMR
): δ ϭ 20.1, 54.6, 60.5, 63.1, 118.9, 126.5,
26.7, 127.4, 128.3, 128.5, 128.8, 131.0, 137.6, 141.3, 168.0 ppm.
(100.62 MHz, CDCl
3
1
[10]
T. Kondo, K. Kodoi, T. Mitsudo, Y. Watanabe, J. Chem. Soc.,
Chem. Commun. 1994, 755Ϫ756.
[11]
ϩ
GC-MS (70 eV): m/z (%) ϭ 264 (0) [M ], 130 (100), 129 (50), 115
Ϫ1
(
20), 105 (22), 77 (21). IR (film): ν˜ ϭ 3060 cm , 2980, 1735, 1450.
K. Matsushita, T. Komori, S. Oi, Y. Inoue, Tetrahedron Lett.
1
trans-11nЈ: Yield 89 mg (32%), oil. H NMR (400.13 MHz,
CDCl ): δ ϭ 1.31 (d, J ϭ 7.2 Hz, 3 H), 3.62 (dd, J ϭ 7.6, 2.2 Hz,
1
994, 35, 5889Ϫ5890.
H. Alper, D. Leonard, J. Chem. Soc., Chem. Commun. 1985,
511Ϫ512.
[12]
3
1
5
H), 4.05 (d, J ϭ 2.2 Hz, 1 H), 5.06 (q, J ϭ 7.2 Hz, 1 H),
.15Ϫ5.26 (m, 2 H), 5.77Ϫ5.86 (m, 1 H), 7.20Ϫ7.33 (m, 10 H)
[
[
[
13]
14]
15]
Y. Imada, H. Alper, J. Org. Chem. 1996, 61, 6766Ϫ6767.
J. Q. Zhou, H. Alper, J. Org. Chem. 1992, 57, 3328Ϫ3331.
D. R. Wagle, M. G. Monteleone, L. Krishnan, M. S. Manhas,
A. K. Bose, J. Chem. Soc., Chem. Commun. 1989, 915.
Y. S. Lo, J. C. Sheehan, J. Am. Chem. Soc. 1972, 94, 8253.
T. Jen, J. Frazee, J. R. E. Hoover, J. Org. Chem. 1973, 38, 2857.
H. E. Applegate, C. M. Cimarusti, W. A. Slusarchyk, Tetra-
hedron Lett. 1979, 1637.
T. F. Buckley, H. Rapoport, J. Am. Chem. Soc. 1982, 104, 4446.
J. C. Sheehan, Y. S. Lo, J. Org. Chem. 1973, 38, 3227.
J. J. Tufariello, D. J. P. Pinto, A. S. Milowsky, D. V. Reinhardt,
Tetrahedron Lett. 1987, 28, 5481.
13
ppm. C NMR (100.62 MHz, CDCl
3
): δ ϭ 18.6, 52.0, 60.7, 63.2,
1
1
1
2
19.0, 126.7, 127.2, 127.7, 128.5, 128.6, 128.7, 130.7, 138.9, 139.8,
68.2 ppm. GC-MS (70 eV): m/z (%) ϭ 264 (0) [M ], 130 (100),
29 (50), 115 (20), 105 (22), 77 (21). IR (film): ν˜ ϭ 3060 cm
980, 1735, 1450.
ϩ
[16]
Ϫ1
,
[17]
[18]
1
1
-(2-Methoxy-1-phenylethyl)-4-phenyl-3-vinylazetidin-2-one (trans-
1o): Yield 160 mg (52%), solid. M.p. 97.2Ϫ99.2 °C (n-hexane). H
[19]
1
[20]
[21]
NMR (400.13 MHz, CDCl
3
): δ ϭ 3.40 (s, 3 H), 3.61 (dd, J ϭ 7.9,
.0 Hz, 1 H), 3.69 (dd, J ϭ 6.9, 2.4 Hz, 1 H), 4.22 (d, J ϭ 2.0 Hz,
H), 4.28Ϫ4.33 (m, 2 H), 5.25 (dd, J ϭ 19.0, 10.4 Hz, 2 H),
2
1
5
[
[
[
[
22]
23]
24]
25]
H. Tanaka, A. K. M. Abdul Hai, M. Sadakane, H. Okumoto,
S. Torii, J. Org. Chem. 1994, 59, 3040Ϫ3046.
S. Calet, F. Urso, H. Alper, J. Am. Chem. Soc. 1989, 111,
13
.90Ϫ5.98 (m, 1 H), 7.19Ϫ7.36 (m, 10 H) ppm. C NMR
): δ ϭ 58.7, 59.0, 60.4, 63.4, 73.0, 119.0, 126.6,
27.4, 127.8, 128.3, 128.6, 128.7, 131.0, 137.5, 137.6, 168.1 ppm.
(
100.62 MHz, CDCl
3
931Ϫ934.
1
ϩ
W. Chamchaang, A. R. Pinhas, J. Org. Chem. 1990, 55,
GC-MS (70 eV): m/z (%) ϭ 307 (0) [M ], 262 (10), 240 (21), 194
27), 130 (100), 129 (81), 115 (50), 91 (28). IR (CHCl
): ν˜ ϭ 3060
cm , 3030, 2920, 2850, 1600, 1520, 1490, 1430, 1340, 1310, 1110,
2943Ϫ2950.
(
3
G. W. Spears, K. Nakanishi, Y. Ohfune, Synlett 1991, 91.
M. E. Piotti, H. Alper, J. Am. Chem. Soc. 1996, 118, 111Ϫ116.
H. Alper, D. Delledonne, M. Kameyama, D. Roberto, Or-
ganometallics 1990, 9, 762Ϫ765.
H. Alper, N. Hamel, Tetrahedron Lett. 1987, 28, 3237Ϫ3240.
M. Mori, K. Chiba, M. Okita, Y. Ban, J. Chem. Soc., Chem.
Commun. 1979, 698.
Ϫ1
[26]
[27]
960, 760, 730, 690. C20
2
H21NO (307.39): calcd. C 78.14, H 6.89, N
4
.55; found C 78.10, H 7.02, N 4.50. trans-11oЈ: Yield 123 mg
1
[28]
(40%), oil. H NMR (400.13 MHz, CDCl
3
): δ ϭ 3.25 (s, 3 H), 3.43
[29]
(dd, J ϭ 9.3, 5.4 Hz, 1 H), 3.60 (dd, J ϭ 8.0, 2.0 Hz, 1 H), 3.75 (t,
J ϭ 9.3 Hz, 1 H), 4.24 (d, J ϭ 2.0 Hz, 1 H), 4.81 (dd, J ϭ 9.3,
.4 Hz, 1 H), 5.18Ϫ5.23 (m, 2 H), 5.83Ϫ5.97 (m, 1 H), 7.22Ϫ7.34
[
[
30]
31]
K. Chiba, M. Mori, Y. Ban, Tetrahedron 1985, 41, 387.
M. Mori, K. Chiba, M. Okita, I. Kayo, Y. Ban, Tetrahedron
5
(
m, 10 H) ppm. 1 C NMR (100.62 MHz, CDCl
3
3
): δ ϭ 57.8, 58.5,
1985, 41, 375.
6
1
2.3, 63.2, 72.0, 119.0, 126.6, 126.8, 127.8, 127.9, 128.3, 128.6,
[32]
Z. Zhou, H. Alper, J. Org. Chem. 1996, 61, 1256Ϫ1260.
S. Torii, H. Okumoto, M. Sadakane, A. K. M. A. Hai, H.
Tanaka, Tetrahedron Lett. 1993, 34, 6553.
H. Tanaka, A. K. M. A. Hai, M. Sadakane, H. Okumoto, S.
Torii, J. Org. Chem. 1994, 59, 3040.
J. Tsuji, J. Kiji, S. Imamura, M. Morikawa, J. Am. Chem. Soc.
964, 86, 4350Ϫ4353.
W. T. Dent, R. Long, G. H. Whitfield, J. Chem. Soc. 1964,
588Ϫ1594.
J. H. Merrifield, J. P. Godschalx, J. K. Stille, Organometallics
1984, 3, 1108Ϫ1112.
S. Murahashi, Y. Imada, Y. Taniguchi, S. Higashiura, J. Org.
Chem. 1993, 58, 1538Ϫ1545.
S. Murahashi, Y. Imada, Y. Taniguchi, S. Higashiura, Tetra-
hedron Lett. 1988, 29, 4945Ϫ4948.
30.9, 136.7, 138.6, 168.7 ppm. GC-MS (70 eV): m/z (%) ϭ 307 (0)
[33]
ϩ
[M ], 262 (10), 240 (21), 194 (27), 130 (100), 129 (81), 115 (50), 91
Ϫ1
(
28). IR (film): ν˜ ϭ 3060 cm , 3030, 2920, 2850, 1600, 1520, 1490,
[34]
1430, 1340, 1310, 1110, 960, 760, 730, 690.
[
[
35]
36]
1
Acknowledgments
1
This work was carried out within the framework of the National
Project ‘‘Stereoselezione in sintesi Organica: Metodologie ed Ap-
plicazioni’’ supported by the Ministero dell’Istruzione, dell’Univer-
sit a` e della Ricerca, Rome. We also thank the Italian Consorzio
Interuniversitario Nazionale ‘‘Metodologie e Processi Innovativi di
Sintesi’’ (CINMPIS), Bari and the University of Lecce for finan-
cial support.
[37]
[
[
[
[
[
[
38]
39]
40]
41]
42]
43]
J. Tsuji, Y. Kobayashi, H. Kataoka, T. Takahashi, Tetrahedron
Lett. 1980, 21, 1475Ϫ1478.
J. Tsuji, K. Sato, H. Okumoto, J. Org. Chem. 1984, 49,
[
[
1]
2]
H. M. Colquhoun, D. J. Thompson, M. V. Twigg, Car-
bonylation, Plenum Press: New York, 1991.
I. Ojima, M. Tzamarioudaki, Z. Li, R. J. Donovan, J. Chem.
Rev. 1996, 96, 635.
F. Ungvary, Coord. Chem. Rev. 1998, 170, 245.
Y. Tamaru, M. Hojo, Z. Yoshida, J. Org. Chem. 1991, 56,
1341Ϫ1344.
J. Tsuji, K. Sato, H. Okumoto, Tetrahedron Lett. 1982, 23,
5189Ϫ5190.
B. M. Trost, N. R. Schmuff, M. J. Miller, J. Am. Chem. Soc.
1980, 102, 5979Ϫ5981.
L. Wartski, Bull. Soc. Chim. France 1975, 1663.
W. Guangzhong, I. Shimoyama, E. Negishi, J. Org. Chem.
1991, 56, 6506Ϫ6507.
L. De Vitis, S. Florio, C. Granito, L. Ronzini, L. Troisi, T.
Pilati, Tetrahedron in press, and available from the correspond-
ing author on request.
[
[
3]
4]
[44]
[45]
1
099Ϫ1105.
G. Lenoble, M. Urrutigo ¨ı ty, P. Kalck, Tetrahedron Lett. 2001,
2, 3697Ϫ3700.
[
[
[
5]
6]
7]
[46]
4
E. Yoneda, S. W. Zhang, K. Onitsuka, S. Takahashi, Tetra-
hedron Lett. 2001, 42, 5459Ϫ5461.
B. El Ali, H. Alper, J. Org. Chem. 1991, 56, 5357Ϫ5360.
Received October 21, 2003
1362
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1357Ϫ1362