Pd-catalyzed one-pot coupling of allylamines, activated alkenes, and unsaturated halides (or triflate): An atom efficient synthesis of highly functionalized pyrrolidines

Article abstract of DOI:10.1016/j.jorganchem.2004.07.039

A Pd-catalyzed three-component assembling of highly functionalized 4-benzyl-(and allyl-)pyrrolidines was achieved based on a combination of allyl amines, gem-diactivated alkenes, and unsaturated halides (or triflate).

Full text of DOI:10.1016/j.jorganchem.2004.07.039

Journal of Organometallic Chemistry 689 (2004) 3831–3836
www.elsevier.com/locate/jorganchem
Pd-catalyzed one-pot coupling of allylamines, activated alkenes,
and unsaturated halides (or triflate): an atom efficient synthesis
of highly functionalized pyrrolidines
a,b
Luc Martinon , Stephane Azoulay , Nuno Monteiro , E. Peter Kundig ,
a
a
b
´
¨
a,
*
`
Genevieve Balme
a
´
Laboratoire de Chimie Organique 1, CNRS UMR 5181, Universite Claude Bernard-Lyon 1, CPE, 43 Bd du 11 Novembre 1918,
F-69622 Villeurbanne, France
b
Department of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, CH-1211 Geneva, Switzerland
Received 14 May 2004; accepted 20 July 2004
Available online 11 September 2004
Abstract
A Pd-catalyzed three-component assembling of highly functionalized 4-benzyl-(and allyl-)pyrrolidines was achieved based on a
combination of allyl amines, gem-diactivated alkenes, and unsaturated halides (or triflate).
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Palladium; Multicomponent reaction; Carbocyclization; Pyrrolidines
1. Introduction
the alkyne moiety via carbopalladation/reductive elimi-
nation (Scheme 1).
Multicomponent assembling processes are drawing
increasing attention in the search for atom efficient,
environmentally friendly new synthetic methodologies.
They have found widespread applications in the prepa-
ration of compound libraries and, to a lesser extent, in
target directed synthesis [1]. Pd-catalyzed cascade proc-
esses are now well-established as powerful tools for the
development of new multicomponent reactions [2]. In
this area, we have recently reported the three-compo-
nent assembling of various oxygen [3,4] and nitrogen
[5] heterocycles by hetero-Michael conjugate addition/
cyclization sequences involving propargylic alcohols
and amines, gem-diactivated alkenes, and unsaturated
halides (and triflates). The key step in this one-pot trans-
formation is the Pd-mediated cyclofunctionalization of
Interestingly, this reaction may also be applied to the
cyclofunctionalization of alkenes but these are generally
much less reactive [6]. In fact, when propargylic alcohols
are substituted for their allylic analogs, the above-men-
tionned three-component reaction becomes rather slug-
gish and low yielding. Besides, non-negligeable
amounts of side products are formed [3,7]. We now wish
to report that reactions involving allylic amines do not
suffer from such drawbacks and allow the clean and
selective assembling of 4-benzylpyrrolidines in moderate
to good yields [8].
2. Results and discussion
In order to probe the participation of allylamines as
nucleophilic partners in the three-component reaction,
preliminary assays were conducted using equimolar
*
Corresponding author. Tel.: +4 72 43 14 16; fax: +4 72 43 12 14.
E-mail address: balme@univ-lyon1.fr (G. Balme).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.07.039

3832
L. Martinon et al. / Journal of Organometallic Chemistry 689 (2004) 3831–3836
R
EWG
EWG
R'
EWG
EWG
R
EWG
EWG
base
Pd
X
RX
cat. Pd0
YH
R'
Y
Y
R'
Y = O, NMe, NBn
EWG = CO2R, SO2Ph
Scheme 1.
amounts of the commercially available N-methylallyl-
amine (1a), dimethyl benzylidene malonate (2a) and
iodobenzene (3a) using reaction conditions similar to
those previously used for the synthesis of 4-benzylidene-
pyrrolidine (5) from N-methylpropargylamine (1.1
equiv. NaH, 5 mol% Pd(0) generated by reduction of
PdCl2(PPh3)2 with n-BuLi, THF-DMSO, room temper-
ature). Following this procedure, we were pleased to ob-
tain the expected 4-benzylpyrrolidine (4a) in 70%
isolated yield with a diastereomeric ratio of 85:15 in fa-
vor of the trans isomer as determined by NMR experi-
ments (NOESY) (Scheme 2, Eq. (1)). It deserves
mention that the corresponding cis isomer can be selec-
tively prepared in two steps upon hydrogenation of 4-
benzylidenepyrrolidine (5) using Pd/C in ethyl acetate
(the trans isomer was not detected in the 1H NMR
(300 MHz) spectra of the crude product) (Scheme 2,
Eq. (2)). This observation demonstrates how by simply
varying the nature of one of the building blocks (i.e.,
the amine) our multicomponent reaction may open ac-
cess not only to different compounds but also, through
hydrogenation, to different stereoisomers of a same
compound.
The participation of alkenes bearing activating
groups other than esters was also investigated. For in-
stance, a-sulfonyl ester (2c) led to the isolation of a mix-
ture of three diastereomeric 3-sulfonylpyrrolines (4c) in
60% yield. The trans relationship at C-2 and C-3 in
the two major isomers (phenyl group anti to the sulfonyl
group) was deduced from NMR experiments and are
consistent with our previous work on similar structures
[8]. Again, 1,3-diastereoselectivity was in favor of the
trans isomer (Table 1, entry 3). Unfortunately, the ster-
eochemistry of the minor third isomer could not be as-
signed. We also found that a vinyl bromide or triflate
could be used in place of the aryl iodides which opens
access to 4-allylpyrrolidines (entries 5, 6). For instance,
reaction of cyclohexenyl triflate (3c) with N-methylallyl-
amine (1a), and dimethyl benzylidene malonate (2a) fur-
nished 4-cyclohexenylpyrrolidine (4f), which was
obtained as a single trans diastereomer (one diastereo-
1
mer detected by 300 MHz H NMR), in 90% isolated
yield (Table 1, entry 6).
We next examined the use of commercially available
diallylamine (1b) as nucleophilic partner as we antici-
pated that the corresponding N-allylpyrrolidines could
then be deprotected to allowing further manipulations.
We were pleased to find that, indeed, 1b participated
in the cyclization process with different conjugate accep-
tors and aryl iodides to yield the desired pyrrolidines
with 1,3-diastereomeric ratios slightly in favor of the
trans isomer (trans:cis = 55:45) (Table 1, entries 7–9).
In conclusion, we have shown that the sequential het-
ero-Michael conjugate addition/carbopalladation/reduc-
tive elimination process recently developed in our
laboratories may also involve allylamines as nucleophi-
lic partners which opens a new and straightforward
The generality of the cyclization process was explored
with various allylamines, alkenes, and organic halides
(Table 1). The nicotine derivative 4b was produced in
65% yield from the corresponding 2-pyridyl alkene
(2b) with a diastereomeric ratio identical to that ob-
tained for 4a (Table 1, entry 2). In the other hand, reac-
tion of triester 2d led to the formation of proline ester
derivative 4d as a single trans diastereomer, as indicated
1
by the H NMR (300 MHz) spectra of the crude reac-
tion product, albeit in a moderate 40% yield (Table 1,
entry 4).
1/ NaH (1 equiv.)
2/ [PdCl2(PPh3)2/2 nBuLi]
CO2Me
CO2Me
Ph
Ph
CO2Me
MeO2C
+
(5 mol%)
(1)
+
PhI
N
NH
Me
THF/DMSO, r.t.
70%
Ph
Me
1a
2a
3a
trans-4a (dr 85:15)
CO2Me
CO2Me
CO2Me
CO2Me
Ph
Ph
as
Pd/C
(2)
+ 2a + 3a
Ph
NH
Me
Ph
H2 (5 atm)
AcOEt, r.t.
95%
above
65%
N
N
Me
Me
5
cis-4a (dr > 95:5)
Scheme 2.

L. Martinon et al. / Journal of Organometallic Chemistry 689 (2004) 3831–3836
3833
Table 1
Three-component synthesis of 4-benzyl pyrrolidinesa
Entry
Allyl amine
Activated olefin
MeO2C CO2Me
Halide (or triflate)
d.r.b trans/cis
Product
Yield
70%
CO2Me
CO2Me
1
85/15
85/15
NH
Me
I
N
2a
CO2Me
3a
1a
Me
4a
MeO2C
CO2Me
CO2Me
N
1a
1a
3a
2
3
65%
N
N
Me
2b
4b
O
O
S
O
O
CO2Me
S
Ph
Ph
60%c
CO Me
2
70/30
3a
3a
N
2c
Me
4c
4d
CO Et
2
EtO C
CO Et
2
2
CO Et
2
1a
1a
4
5
>95/5
75/25
40%
66%
CO Me
CO Me
2
2
N
2d
CO2Et
Me
EtO2C
Ph
CO2Et
CO2Et
Ph
Br
3b
N
F
Me
2e
F
4e
CO Me
2
CO Me
2
1a
6
7
>95/5
55/45
55/45
2a
2a
90%
51%
OTf
N
3c
Me
4f
CO Me
2
CO Me
2
3a
N
N
H
1b
4g
O
S
O
Ph
CO Me
2
1b
1b
3a
2c
2c
65%
40%
8
N
4h
Ph
O
O
S
MeO
MeO
CO Me
2
9
55/45
N
I
3d
4i
a
All reactions were performed on a 1.05 mmol scale.
1,3-Diastereoselectivity.
Contains approximately 10% of an uncharacterized third diastereomer.
b
c

3834
L. Martinon et al. / Journal of Organometallic Chemistry 689 (2004) 3831–3836
acces to diversely functionalized 4-benzyl (and 4-allyl)
pyrrolidines. In addition, this versatile and atom-eco-
nomical method may allow to access different isomers
of the latter compounds depending on the nature of
the starting amine (allylic or propargylic). Further stud-
ies are in progress in our laboratories to explore the
potential of these highly functionalized pyrrolidines as
synthetic scaffolds for derivatization chemistry.
Dimethyl ( )-(2RS,4RS)-4-benzyl-1-methyl-2-phe-
nylpyrrolidine-3,3-dicarboxylate (trans-4a): Colorless
solid (m.p.: 73–74 ꢁC). H NMR (300 MHz, C6D6): d
1
2.20 (s, 3H), 2.32 (t, J = 12.8 Hz, 1H), 2.45 (dd,
J = 8.8, 10.7 Hz, 1H), 3.00 (s, 3H), 3.15 (dd, J = 6.2,
8.8 Hz, 1H), 3.36 (dd, J = 3.8, 12.8 Hz, 1H), 3.45 (s,
3H), 3.95 (m, 1H), 4.74 (s, 1H), 7.13–7.63 (m, 10H).
13C NMR (75 MHz, C6D6): d 37.1, 40.3, 46.4, 51.7,
51.9, 60.5, 69.7, 76.6, 126.7, 127.6, 128.0, 128.2, 128.3,
128.5, 129.0, 129.2, 129.4, 140.9, 170.0, 171.3. Anal.
Calc. for C18H25NO4 (319.40): C, 71.42; H, 6.87. Found:
C, 71.71; H, 6.77%.
3. Experimental
3.1. General
Dimethyl ( )-(2RS,4SR)-4-benzyl-1-methyl-2-phe-
nylpyrrolidine-3,3-dicarboxylate (cis-4a): Selected data
deduced from a mixture of diastereomers: 1H NMR
(300 MHz, C6D6): d 2.13 (s, 3H), 2.52 (t, J = 9.3 Hz,
1H), 2.84 (m, 1H), 3.13 (s, 3H), 3.46 (s, 3H), 3.47 (t,
J = 7.3 Hz, 2H), 3.66 (dd, J = 7.7, 9.3 Hz, 1H), 4.50 (s,
1H), 7.13–7.94 (m, 10H). 13C NMR (75 MHz, C6D6):
d 37.0, 40.8, 47.6, 51.3, 52.0, 59.2, 69.0, 76.0, 126.6,
126.7, 127.6, 127.9, 128.2, 128.5, 129.0, 129.2, 129.3,
129.5, 141.6, 167.9, 171.3.
Unless otherwise noted, all reactions were carried
out under a nitrogen atmosphere using standard syr-
inge, cannula, and septa techniques. Commercially
available reagents were used as purchased. THF and
DMSO were distilled over calcium hydride. TLC was
carried out on Merck silica 60/F-254 aluminium-
backed plates. Flash chromatography was performed
using Merck silica gel 60 (40–63 lm). Melting points
were determined on a Buchi and are uncorrected.
¨
NMR spectra were recorded on a Brucker ALS 300
spectrometer in the solvent indicated. Chemical shifts
d are reported in ppm relative to the internal
reference.
Dimethyl ( )-(2RS,4RS)-4-benzyl-1-methyl-2-pyri-
dinepyrrolidine-3,3-dicarboxylate (trans-4b): Pale yel-
low solid (m.p.: 70–71 ꢁC). 1H NMR (300 MHz,
CDCl3): d 2.13 (t, J = 12.6 Hz, 1H), 2.20 (s, 3H),
2.33 (dd, J = 9.2, 10.8 Hz, 1H), 3.04–3.10 (m, 2H),
3.16 (s, 3H), 3.48–3.52 (m, 1H), 3.82 (s, 3H), 4.39
(s, 1H), 7.23–7.35 (m, 7H), 7.68 (d, J = 7.9 Hz, 1H),
8.53 (m, 2H). 13C NMR (75 MHz, CDCl3): d 36.5,
40.6, 45.9, 52.3, 52.8, 60.2, 69.3, 73.6, 126.8, 128.9,
129.0, 136.3, 140.1, 149.5, 150.9, 169.8, 171.0. CIMS:
369 (MH+).
Dimethyl ( )-(2RS,4SR)-4-benzyl-1-methyl-2-pyri-
dinepyrrolidine-3,3-dicarboxylate (cis-4b): Oil. 1H
NMR (300 MHz, CDCl3): d 2.16 (s, 3H), 2.60 (t,
J = 9.5 Hz, 1H), 2.85–2.92 (m, 1H), 3.04 (t, J = 12.5
Hz, 1H), 3.13 (dd, J = 3.8, 12.5 Hz, 1H), 3.37 (s,
3H), 3.41 (dd, J = 2.5, 9.5 Hz, 1H), 3.80 (s, 3H),
4.22 (s, 1H), 7.18–7.85 (m, 6H), 7.86 (d, J = 7.5 Hz,
1H), 8.52 (s, 1H), 8.71 (s, 1H). 13C NMR (75 MHz,
CDCl3): d 36.7, 41.2, 46.9, 52.1, 53.0, 59.2, 68.8,
74.0, 126.7, 129.0, 129.1, 137.0, 140.9, 149.3, 150.8,
168.0, 171.2.
3.2. General procedure for the preparation of the pyrrol-
idines 4
3.2.1. Preparation of the Pd(0) catalyst
n-BuLi (2.0 M in hexanes, approx. 50 ll, 0.1 mmol)
was added dropwise to a well stirred suspension of
PdCl2(PPh3)2 (35 mg, 0.05 mmol) in DMSO (2.5 ml) un-
til a dark red homogeneous solution was obtained.
3.2.2. Three-component reaction
The allylamine (1.05 mmol) was slowly added to a
well stirred suspension of NaH (60% in mineral oil, 44
mg, 1.05 mmol) in THF (3 ml) and stirring was contin-
ued for 5 min. The activated alkene (1.05 mmol) was
then added and the resulting enolate solution was stirred
at room temperature for an additional 5 min. Mean-
while, the unsaturated iodide or triflate (1.07 mmol)
was added to the freshly prepared palladium complex
solution and this was subsequently transferred via cann-
ula to the enolate solution. The resulting reaction mix-
ture was stirred overnight at room temperature and
then washed with NaHCO3 (2 · 5 ml), brine (3 ml)
and water (3 ml). The aqueous phases were extracted
with CH2Cl2 (3 · 15 ml) and the combined organic lay-
ers were dried over Na2SO4 and concentrated in vacuo.
The residue was subjected to silica gel chromatography
(ethyl acetate: petroleum ether) to afford the desired
pyrrolidines.
Methyl ( )-(2RS,3SR,4SR)3-benzenesulfonyl-4-ben-
zyl-1-methyl-2-phenylpyrrolidine-3-carboxylate (trans-4c):
1
Orange solid (m.p.: 144–145 ꢁC). H NMR (300 MHz,
CDCl3): d 2.23 (s, 3H), 3.01–3.09 (m, 1H), 3.12–3.16
(m, 1H), 3.14 (s, 3H), 3.35–3.52 (m, 2H), 3.73–3.81 (m,
1H), 4.17 (s, 1H), 7.06–8.15 (m, 10 H). 13C NMR (75
MHz, CDCl3): d 34.4, 40.6, 50.1, 52.3, 58.8, 75.9, 86.9,
126.6, 128.4, 128.7, 129.4, 132.8, 134.5, 139.4, 139.7,
142.0, 167.0.
Diethyl ( )-(2SR,4RS)-4-benzyl-2-methoxycarbonyl-
1-methylpyrrolidine-3,3-dicarboxylate (trans-4d): Color-
1
less oil. H NMR (300 MHz, CDCl3): d 1.22–1.32 (m,

L. Martinon et al. / Journal of Organometallic Chemistry 689 (2004) 3831–3836
3835
6H), 2.15 (t, J = 12.7 Hz, 1H), 2.40 (dd, J = 8.9, 10.9 Hz,
1H), 2.44 (s, 3H), 2.94 (dd, J = 6.4, 8.9 Hz, 1H), 3.26
(dd, J = 3.4, 12.7 Hz, 1 H), 3.68 (s, 3H), 3.91 (s, 1H),
3.31–3.45 (m, 1H), 4.07–4.30 (m, 4H), 7.18–7.29 (m,
5H). 13C NMR (75 MHz, CDCl3): d 14.3, 14.6, 36.2,
41.6, 46.8, 52.5, 59.9, 62.0, 62.4, 65.8, 73.7, 126.7,
128,8, 129.0, 140.4, 169.2, 170.0. Anal. Calc. for
C20H27NO6 (377.43): C, 63.65; H, 7.21. Found: C,
63.70; H, 7.39%.
Methyl ( )-(2RS,3SR,4SR)-1-Allyl-3-benzenesulfo-
nyl-4-benzyl-2-phenylpyrrolidine-3-carboxylate (trans-4h):
Brown solid (m.p.: 155–156 ꢁC). H NMR (300 MHz,
1
CDCl3): d 2.48 (dd, J = 2.3 Hz, J = 13.2 Hz, 1H), 2.68
(dd, J = 11.3, 13.2 Hz, 1H), 2.75 (dd, J = 7.9, 9.8 Hz,
1H), 3.00 (dd, J = 6.8, 14.0 Hz, 1H), 3.23 (s, 3H),
3.29–3.39 (m, 3H), 4.96 (s, 1H), 5.03–5.19 (m, 2H),
5.71–5.85 (m, 1H), 7.06 (d, J = 7.1 Hz, 1H), 7.21–7.30
(m, 7H), 7.41 (d, J = 7.2 Hz, 2H), 7.59 (t, J = 7.5 Hz,
2H), 7.70 (t, J = 7.3 Hz, 1H), 8.22 (d, J = 7.3 Hz, 2H).
13C NMR (75 MHz, CDCl3): d 36.5, 46.7, 51.6, 57.5,
66.0, 72.3, 86.9, 117.3, 126.6, 127.7, 127.8, 128.5,
128.7, 128.9, 131.7, 134.3, 135.5, 138.5, 138.8, 139.9,
166.2.
Methyl ( )-(2RS,3SR,4RS)-1-Allyl-3-benzenesulfo-
nyl-4-benzyl-2-phenylpyrrolidine-3-carboxylate carboxy-
late (cis-4h): Brown solid (m.p.: 131–132 ꢁC).1H
NMR (300 MHz, CDCl3): d 2.85 (dd, J = 8.3, 13.5
Hz, 1H), 2.97 (t, J = 8.3 Hz, 1H), 3.04 (s, 3H), 3.08–
3.15 (m, 2H), 3.29 (t, J = 12.4 Hz, 1H) 3.42 (dd,
J = 2.8, 13.5 Hz, 1H), 3.62–3.70 (m, 1H), 4.32 (s,
1H), 4.97 (s, 1H), 5.01 (d, J = 5.2 Hz, 1H), 5.62–5.76
(m, 1H), 6.95–7.67 (m, 13H), 8.02 (d, J = 7.2 Hz,
2H). 13C NMR (75 MHz, CDCl3): d 29.8, 34.17,
49.30, 52.0, 55.1, 55.6, 86.2, 126.2, 127.8, 128.0,
128.4, 128.6, 128.7, 128.8, 129.0, 132.4, 134.2, 134.7,
139.3, 141.6, 166.6.
Dimethyl ( )-(2RS,4RS)-2-(4-fluoro-phenyl)-1-me-
thyl-4-(1-phenylpropen-1-yl)pyrrolidine-3,3-dicarboxylate
(cis- and trans-4e): Inseparable mixture of diastereo-
mers: Colorless oil. 1H NMR (300 MHz, CDCl3): d
0.74 (t, J = 7.2 Hz, 2.25H), 0.79 (t, J = 7.1 Hz, 0.75
H), 1.27 (t, J = 7.0 Hz, 3H), 2.15 (s, 3H), 2.53–2.60
(m, 1H), 2.70 (d, J = 9.2 Hz, 1H), 3.20–3.34 (m,
2H), 3.69–3.78 (m, 0.75 H), 3.80–3.86 (m, 0.25 H),
4.08–4.27 (m, 4H), 4.15 (s, 0.25 H), 4.21 (s, 0.75 H),
6.08–6.18 (m, 1H), 6.37 (d, J = 15.8 Hz, 0.75 H),
6.41 (d, J = 16.0 Hz, 0.25 H), 6.91 (t, J = 8.7 Hz,
2H), 7.16 (t, J = 7.0 Hz, 1H), 7.21–7.30 (m, 6H). 13C
NMR (75 MHz, CDCl3): d 13.4, 13.5, 14.1, 33.7,
34.1, 40.2, 40.8, 43.2, 44.6, 59.1, 60.4, 60.6, 61.0,
2
61.2, 61.3, 67.8, 68.6, 114.4 (2 CH, d, J(C,F) = 21
2
Hz), 114.6 (2 CH, d, J(C,F) = 21 Hz), 126.0–129.0,
3
130.2 (2 CH, d, J(C,F) = 8 Hz), 130.4 (2 CH, d,
4
3J(C,F) = 8 Hz), 131.3, 131.5, 133.7 (C, d, J(C,F) = 3
4
Hz), 135.5 (C, d, J(C,F) = 3 Hz), 137.3, 137.5, 162.3
Methyl ( )-(2RS,3SR,4SR)-1-Allyl-3-benzenesulfo-
nyl-4-(4-methoxy-benzyl)-2-phenylpyrrolidine-3-carboxy-
1
1
(C, d, J(C,F) = 245 Hz), 162.4 (C, d, J(C,F) = 245
Hz), 167.3, 169.8, 170.2, 170.7.
1
late (trans-4i): Colorless solid (m.p.: 153–154 ꢁC). H
Dimethyl ( )-(2RS,4RS)-4-cyclohexenyl-1-methyl-2-
phenylpyrrolidine-3,3-dicarboxylate (trans-4f): Colorless
solid (m.p.: 75–76 ꢁC).1H NMR (300 MHz, CDCl3): d
1.56–1.65 (m, 5H), 1.86–1.93 (m, 1H), 2.00 (s, 2H),
2.15–2.29 (m, 2H), 2.22 (s, 3H), 3.03 (s, 3H), 3.25–3.30
(m, 1H), 3.35–3.48 (m, 1H), 3.74 (s, 3H), 4.26 (s, 1H),
5.47 (s, 1H), 7.19–7.32 (m, 5H). 13C NMR (75 MHz,
CDCl3): d 22.2, 23.2, 25.4, 28.0, 38.8, 40.6, 41.9, 60.6,
76.2, 123.2, 127.7, 128.0, 128.6, 135.6, 139.8, 170.1,
171.1. Anal. Calc. for C22H29NO4 (371.48): C, 71.13;
H, 7.87. Found: C, 71.12; H, 7.87%.
NMR (300 MHz, CDCl3): d 2.40 (dd, J = 3.0, 13.6
Hz, 1H), 2.62 (dd, J = 11.3, 13.6 Hz, 1H), 2.89 (dd,
J = 7.5, 9.8 Hz, 1H), 3.00 (dd, J = 6.6, 14.3, 1H),
3.23 (s, 3H), 3.29–3.43 (m, 3H), 3.79 (s, 3H), 4.98 (s,
1H), 5.11 (ddd, J = 1.5, 9.4, 17.3 Hz, 2H), 5.72–5.85
(m, 1H), 6.82 (d, J = 8.7 Hz, 2H), 6.98 (d, J = 8.7
Hz, 2H), 7.20–29 (m, 3 H), 7.43 (d, J = 7.2 Hz, 2H),
7.59 (t, J = 7.9 Hz, 2H), 7.67 (d, 1H), 8.22 (d, J = 8.3
Hz, 2H). 13C NMR (75 MHz, CDCl3): d 35.6, 38.7,
46.9, 51.5, 55.3, 57.5, 72.2, 86.9, 114.0, 117.3, 127.6,
127.8, 128.4, 128.8, 129.6, 131.6, 131.9, 134.3, 135.5,
138.4, 139.2, 158.2, 166.2. CIRMS: 506 (MH+), 366.
HRCIMS: Calc. for C29H32NO5S: 506.2001. Found:
506.2010.
Dimethyl
( )-1-allyl-4-benzyl-2-phenylpyrrolidine-
3,3-dicarboxylate (cis- and trans-4g): Inseparable mix-
ture of diastereomers: colorless solid. 1H NMR (300
MHz, CDCl3): d 2.02 (t, J = 12.6 Hz, 0.55H), 2.20
(dd, J = 9.0, 10.9 Hz, 0.55H), 2.56 (t, J = 9.4 Hz,
0.45H), 2.60–2.68 (m, 0.90H), 2.75–2.81 (dd, J = 7.5,
13.6 Hz, 0.55H), 2.99 (s, 3H), 3.01–3.11 (m, 1H), 3.17
(s, 1.1H), 3.37–3.49 (m, 0.90H), 3.78 (s, 3H), 4.53 (s,
1H), 4.99–5.11 (m, 2H), 5.70–5.84 (m, 1H), 7.15–7.44
(m, 10 H). 13C NMR (75 MHz, CDCl3): d 36.5, 46.1,
47.6, 52.6, 52.8, 56.6, 56.7, 68.5, 68.9, 73.4, 73.8,
117.3, 126.7, 128.0, 128.2, 128.9, 129.1, 129.3, 135.4,
136.0, 140.6, 168.2, 170.04, 171.5. Anal. Calc. for
C24H27NO4: C, 73.25; H, 6.92. Found: C, 73.43; H,
7.13%.
Methyl ( )-(2RS,3SR,4RS)-1-Allyl-3-benzenesulfo-
nyl-4-(4-methoxybenzyl)-2-phenylpyrrolidine-3-carboxy-
1
late (cis-4i): Brown solid (m.p.: 131–132 ꢁC). H NMR
(300 MHz, CDCl3): d 2.91–2.99 (m, 1H), 3.05–3.22 (m,
3H), 3.14 (s, 3H), 3.29–3.48 (m, 2H), 3.68–3.76 (m,
1H), 3.84 (s, 3H), 4.42 (s, 1H), 5.07 (s, 1H), 5.12 (d,
1H), 5.73–5.87 (m, 1H), 6.61 (s, 2H), 6.89 (d, 2H),
7.04–7.12 (m, 3H), 7.28 (t, 3H), 7.65 (t, 2H), 7.78 (t,
1H), 8.12 (d, 2H). 13C NMR (75 MHz, CDCl3): d
33.3, 49.6, 52.0, 55.2, 55.4, 55.6, 72.5, 86.2, 114.0,
117.7, 127.9, 128.0, 128.1, 128.4, 130.0, 132.5, 133.8,
134.2, 139.4, 158.1, 166.7.

3836
L. Martinon et al. / Journal of Organometallic Chemistry 689 (2004) 3831–3836
[6] (a) For exhaustive illustrations see G. Balme, N. Monteiro, D.
Acknowledgements
Bouyssi, in: E.-I. Negishi (Ed.), Handbook of Organopalladium
Chemistry for Organic Synthesis, Wiley, New York, 2002, p.
2245;
We thank the Swiss National Science Foundation for a
´ ˆ
fellowship (to L.M.) and Region Rhone-Alpes for a grant.
(b) G. Balme, D. Bouyssi, T. Lomberget, N. Monteiro, Synthesis
14 (2003) 2115.
[7] M. Cavicchioli, E. Sixdenier, A. Derrey, D. Bouyssi, G. Balme,
Tetrahedron Lett. 38 (1997) 1763.
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