Chemoselective cross-metathesis reaction between electron-deficient 1,3-dienes and olefins

Article abstract of DOI:10.1016/j.jorganchem.2006.09.026

Chemoselective cross-metathesis reactions between methyl sorbate or 1,3-dienic amides and various olefins in the presence of the Grubbs-Hoveyda catalyst have been investigated. Cross-metathesis reactions turned out to be more chemoselective with 1,3-dienic amides than with 1,3-dienic esters.

Full text of DOI:10.1016/j.jorganchem.2006.09.026

Journal of Organometallic Chemistry 691 (2006) 5456–5465
www.elsevier.com/locate/jorganchem
Chemoselective cross-metathesis reaction between
electron-deficient 1,3-dienes and olefins
´
´
´
Laurent Ferrie, Dominique Amans, Sebastien Reymond, Veronique Bellosta,
*
Patrice Capdevielle, Janine Cossy
Laboratoire de Chimie Organique associe´ au CNRS ESPCI, 10 rue Vauquelin, 75231 Paris Cedex 05, France
Received 7 July 2006; received in revised form 14 September 2006; accepted 14 September 2006
Available online 20 September 2006
Abstract
Chemoselective cross-metathesis reactions between methyl sorbate or 1,3-dienic amides and various olefins in the presence of the
Grubbs–Hoveyda catalyst have been investigated. Cross-metathesis reactions turned out to be more chemoselective with 1,3-dienic
amides than with 1,3-dienic esters.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Cross-metathesis; Methyl sorbate; Dienic amides
1. Introduction
tions have been described between conjugated electron-
deficient olefins such as ethyl sorbate and various olefin
cross-partners [10]. When ethyl sorbate (1) and 5-hexenyl
acetate (2) were heated in refluxing CH2Cl2 in the presence
of catalyst [Ru]-II (10 mol%), 1,3-diene 3 and olefin 4 were
obtained as an inseparable 4/1 mixture (Scheme 1). Indeed,
the ester functionality in ethyl sorbate (1) does not suffi-
ciently deactivate the a,b-double bond towards CM and
thus when [Ru]-II is used, both olefins of the diene react.
By reducing the electron density at the a,b-double bond,
as well as by increasing steric hindrance at the a-carbon,
the CM is more chemoselective [10].
As the phosphine-free ruthenium complex [Ru]-III
exhibits superior activity towards electron-deficient olefins
compared to [Ru]-II [11], we initiated a systematic study
designed to explore the construction of substituted 1,3-
dienes of type A by performing CM reactions between
methyl sorbate (5) and diverse olefin partners. Further-
more, we also investigated the corresponding dienic amides
14–16 in order to increase the chemoselectivity of the CM
reaction, which would result in the selective formation of
dienes of type A and therefore would decrease the forma-
tion of olefins of type B (Scheme 2).
In the last decade, metal-catalyzed olefin metathesis has
emerged as one of the most powerful and reliable organo-
metallic transformations for carbon-carbon bond forma-
tion in organic synthesis [1], and particularly, ring-closing
metathesis (RCM) and cross-metathesis (CM) [2] reactions
have been thoroughly investigated. These convenient syn-
thetic techniques have recently gained prominence due to
the commercial availability of molybdenum catalyst
[Mo]-I [3] and robust ruthenium carbene complexes such
as [Ru]-I [4], [Ru]-II [5], and [Ru]-III [6], which exhibit
good activities, operational simplicity, and remarkable
functional group tolerance (Fig. 1). Therefore, the metath-
esis has become a powerful synthetic tool that has been
widely used in the synthesis of natural products [7].
Although the RCM between 1,3-dienes and olefins has
been used to synthesize complex naturally occurring mole-
cules [8], CM reactions involving conjugated 1,3-dienes
have been scarcely investigated [9]. Only recently, CM reac-
*
Corresponding author. Tel.: +33 1 40 79 44 29; fax: +33 1 40 79 46 60.
E-mail address: janine.cossy@espci.fr (J. Cossy).
0022-328X/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.09.026

L. Ferrie´ et al. / Journal of Organometallic Chemistry 691 (2006) 5456–5465
5457
Mes
N
N
Mes
Mes
N
N
Mes
Ph
PCy3
Ru
i
-Pr
i
-Pr
Cl
Cl
Cl
Cl
Ru
O
N
Me
Ru
F3C
F3C
Cl
Ph
Cl
PCy3
Mo
PCy3
O
Ph
Me
O
[Ru]-III
[Ru]-I
[Ru]-II
F3C
CF3
[Mo]-I
Mes =
Cy = Cyclohexyl
Fig. 1. Commercially available metal carbenes used in RCM and CM reactions.
[Ru]-II
(10 mol%)
OEt
OEt
OEt
+
+
AcO
AcO
AcO
4
4
4
CH2Cl2, reflux
12 h
O
O
O
1
2
3
4
3/4 = 4/1
Scheme 1.
[Ru]-III
R
X
R
X
+
+ R
X
O
O
O
B
A
5 X = OMe
14 X = N( Pr)2
15 X = N(OMe)Me
i
O
S
O
16 X =
N
Scheme 2.
2. CM reactions with methyl sorbate (5)
The CM reaction with electron-deficient olefins such as
methyl vinyl ketone and tert-butyl acrylate was also studied
and, respectively, afforded the CM products 12 and 13 in
poor yields (13–30%) (Table 1, entries 7 and 8) [12].
When methyl sorbate (5) and oct-1-ene (5 equiv.) were
stirred in CH2Cl2 at rt (c = 0.2 M) for 48 h in the presence
of [Ru]-III (5 mol%), the desired conjugated diene 6 was
isolated as an inseparable mixture of (E,E)-6 and (E,Z)-6
stereoisomers in a 10/1 ratio, accompanied by the corre-
sponding mono-olefin of type B (A/B = 2.5/1) with a glo-
bal yield of 68% (Table 1, entry 1). In the case of the
CM between methyl sorbate (5) and allyl trimethylsilane,
dienic ester 7 was obtained as a mixture of stereoisomers
(E,E)-7 and (E,Z)-7 in a 5/1 ratio in addition to being con-
taminated with olefin of type B (A/B = 6/1). When styrene
was used, the conjugated diene 8 was formed in 35% yield
with an excellent stereoselectivity as only the (E,E)-8 iso-
mer was isolated and no trace of the mono-olefin of type
B was observed (Table 1, entry 3) [12].
3. CM with dienic amides
It was hypothesized the kinetics of the CM reaction
with a,b-unsaturated amides was decreased by the chela-
tion of the amide carbonyl group on the ruthenium
center, and therefore, the efficiency of CM between
a,b-unsaturated amides and olefins was affected by the
substituents on the amide nitrogen [13]. Since the dienic
esters did not show good chemoselectivity in CM, we
turned our attention to dienic amides possessing more
electron-rich carbonyl groups. In the case of (E,E)-dienic
amides, easily accessible from sorbic acid [14], the chela-
tion as well as the steric hindrance should avoid the
CM with the a,b-unsaturation and the CM product at
the c,d-position should be obtained selectively. In conse-
quence, CM reactions between dienic amides 14–16 with
a variety of electron-rich olefins were examined. The
results are reported in Table 2.
Other olefins such as diethyl allylphosphonate, allyl bro-
mide and N-allyl-p-toluenesulfonamide were also examined
in the cross-metathesis reaction with methyl sorbate (5). In
each case, the corresponding CM products were formed in
moderate yields (45–56%) and were sometimes accompa-
nied by the mono-olefin of type B (Table 1, entries 4–6) [12].

5458
L. Ferrie´ et al. / Journal of Organometallic Chemistry 691 (2006) 5456–5465
Table 1
ify this hypothesis, compound 18A was treated with catalyst
[Ru]-III (5 mol%) in the presence of 5 equiv. of oct-1-ene
(Scheme 3) [15]. After 4.5 h a negligible amount of monoole-
fin 18B was formed, the main product of the reaction being
dimer C. After 24 h, the amount of dimer C increased with-
out significant augmentation of the monoolefin 18B. How-
ever, at this stage, partial decomposition of 18A was
ascertained. An additional amount of 5 mol% of catalyst
[Ru]-III was subsequently added and after 3 days of stirring
diene 18A was almost totally decomposed and 18B was not
formed anymore. So it seems that the decrease of the 18A/
18B ratio by increasing the reaction time could be due to
the decomposition of diene 18A. Furthermore, when 18A
was stirred alone with catalyst [Ru]-III (10 mol%) for 24 h,
only traces of 18B were detected and no significant decompo-
sition of 18A occurred. However, as the formation of dimer
C was noticed, it seems that catalyst [Ru]-III slowly inserts in
the c,d-double bond of diene 18A. According to these results,
it seems that the main active species is intermediate Z which
principally inserts in the c,d-double bond of amide 15 to give
18A, and to a minor extent in the a,b-double bond of 15 to
give 18B. Finally, by decreasing the amount of catalyst
[Ru]-III and the reaction time, the chemoselectivity can be
improved.
When allyl bromide was involved in the CM reaction
with Weinreb amide 15, for 14 h at rt, with 5 mol% of
[Ru]-III, the corresponding dienic amide 19 was formed
in 39% yield with a very good (E,E)/(E,Z) ratio of 19/1.
Interestingly, no trace of mono-olefin of type B was
detected (Table 2, entry 5). In the case of the CM reaction
between Weinreb amide 15 and (Z)-1,4-dichloro-2-butene
the best results were obtained when the reaction was car-
ried out with 5 mol% of [Ru]-III, at rt for 30 min. Under
these conditions, compound 20 was isolated in 59% yield
[(E,E)/(E,Z) = 32/1] with a A/B ratio of 13/1 (Table 2,
entries 6 and 7). When amide 15 was involved in the
cross-metathesis reaction with 1-acetoxy-but-3-ene, allyltri-
methylsilane, and (Z)-1,4-diacetoxy-but-2-ene, the dienic
cross-metathesis products were isolated as a mixture of
(E,E)- and (E,Z)-stereoisomers. In the case of the CM
between amide 15 and 1-acetoxy-but-3-ene (24 h,
10 mol% [Ru]-III), compound 21 was obtained along with
the corresponding mono-olefin of type B in a 24/1 ratio
and 46% overall yield. With allyltrimethylsilane, the
cross-product 22 was isolated in 45% yield with a (E,E)-
22/(E,Z)-22 ratio of 4/1 and 23 was formed in 42% yield
with a (E,E)-23/(E,Z)-23 ratio of 5/1 when (Z)-1,4-diacet-
oxy-but-2-ene was used in the CM reaction with amide 15
(Table 2, entries 8–10). Interestingly in these three latter
cases, the formation of B was probably kinetically
decreased due to either a complexation of the ruthenium
complex with participation of carbonyl group of the ace-
tate as previously reported [13,16] (Scheme 4; Table 2,
entries 8 and 10) or by steric hindrance of the olefin partner
(Table 2, entry 9).
CM reactions between methyl sorbate (5) and a variety of cross-partners
[Ru]-III
(5 mol%)
R
OMe
+
R
OMe
R
+
OMe
CH2Cl2, rt
48 h
O
O
O
A
B
5
(5 equiv.)
Entry
1
R
Product A
(E,E)/(E,Z)
Ratio A/B
Yielda
Hex
Hex
OMe
2.5/1
68%
6
10/1
O
OMe
OMe
6/1
2
3
TMS
TMS
71%
O
O
7
5/1
35%b,c
Ph
8
100/0
O
O
4
4/1c
OMe
OMe
(EtO)2P
(EtO)2P
56%
9
5.5/1
O
O
48%b,c
5
6
Br
Br
10
32/1
4/1
OMe
OMe
TsHN
TsHN
45%
O
O
11
11.5/1
O
O
O
O
7
8
13%b,c
30%b,c
12
100/0
OMe
t-BuO
t-BuO
O
13
50/1
a Isolated yield for the mixture of A and B.
b No trace of B was detected.
c Atrienic compound was identified by GC/MS and NMR spectroscopy (see Section 5).
When the dienic N,N-diisopropylamide 14 was utilized in
the CM reaction with oct-1-ene (5 equiv.) in the presence of
10 mol% of [Ru]-III at rt for 24 h, the cross-metathesis prod-
uct 17 was isolated in 36% yield in a 28/1 (E,E)/(E,Z) ratio
and no trace of mono-olefin of type B was detected (Table
2, entry 1). Under the same conditions (oct-1-ene, 5 equiv.;
[Ru]-III 10 mol%, CH2Cl2, rt, 24 h), the dienic Weinreb
amide 15 was transformed into the dienic amide 18 [(E,E)/
(E,Z) = 6/1] and into the corresponding mono-olefin of type
B in 65% yield in a 3.5/1 A/B ratio (Table 2, entry 2). In order
to decrease the formation of the mono-olefin of type B, the
amount of the [Ru]-III catalyst was decreased to 5 mol%.
After 24 h, the dienic compound 18 and the mono-olefin of
type B were obtained in 60% yield in a 5/1 ratio, and under
these conditions the (E,E)-18/(E,Z)-18 ratio was 29/1 (Table
2, entry 3). It is worth noting that, when the reaction was
stopped after 1 h, the (E,E)-18 and (E,Z)-18 ratio was
increased to 49/1, the isolated yield of 18 along with the cor-
responding mono-olefin of type B was 64%, and the A/B
ratio was interestingly increased to 13/1 (Table 2, entry 4).
Thus, the increase of the 18A/18B ratio by decreasing the
reaction time seems to indicate that compound 18B would
be formed from the putative kinetic diene 18A, which would
imply an insertion of the [Ru] in its a,b-double bond. To ver-
In the case of more hindered dienic amides such as
camphorsultamide 16,
a good chemoselectivity was

L. Ferrie´ et al. / Journal of Organometallic Chemistry 691 (2006) 5456–5465
5459
Table 2
CM reactions between dienic amides 14–16 and a variety of cross-partners
R1
R1
N
R1
[Ru]-III
R
N
+
+
R
R
N
R2
R2
R2
CH2Cl2, rt
O
O
(5 equiv)
O
A
B
14 - 16
[Ru]-III
R
t (h)
24
diene
A
Ratio A/B
Entry
1
Amide
mol %
(E,E)/(E,Z)
yielda
c
10
10
N
N
36%
5
5
5
O
O
14
15
17
28/1b
Me
N
Me
N
3.5/1
65%
24
2
OMe
OMe
5
O
O
18
6/1
5/1
60%
18
29/1
3
4
15
15
24
1
5
5
5
5
13/1
64%
18
49/1
Me
N
c
5
6
7
15
15
15
14
24
5
10
5
Br
Cl
OMe
39%
Br
19
19/1
O
O
Me
N
2/1
OMe
Cl
Cl
70%
20
18/1
13/1
59%
20
32/1
0.5
Cl
Cl
Me
N
AcO
24/1
46%
OMe
AcO
8
9
15
15
24
24
10
10
21
O
Me
N
7/1
c
45%
TMS
AcO
OMe
TMS
22
O
O
Me
N
4/1b
c
OMe
42%
10
11
15
24
24
10
10
AcO
OAc
23
5/1
O
S
O
O
O
N
S
c
N
61%
5
5
O
O
O
O
24
10/1
16
16
O
O
N
c
S
S
AcO
40%
AcO
AcO
12
13
24
24
10
10
25
9/1
O
O
N
c
16
AcO
40%
OAc
26
5/1
(continued on next page)

5460
L. Ferrie´ et al. / Journal of Organometallic Chemistry 691 (2006) 5456–5465
Table 2 (continued)
[Ru]-III
R
t (h)
24
diene
A
Ratio A/B
Entry
Amide
mol %
(E,E)/(E,Z)
yielda
O
S
O
c
N
57%
Cl
14
16
10
Cl
Cl
27
16/1
O
a Global yield of the mixture of A and B.
b (E,E) and (E,Z) isomers were separated.
c B was not detected by GC/MS and 1H NMR.
[Ru]-III
(5 mol% + 5 mol%)
Me
N
Me
N
Me
N
+
+
OMe
5
OMe
OMe
5
5
5
5
CH2Cl2
O
O
O
18A
18A
18B
C
4,5 h
24 h
traces
traces
partially decomposed
3 days
traces
almost totally
decomposed
[Ru]-III
(10 mol%)
Me
N
Me
N
Me
N
+
+
OMe
5
OMe
OMe
5
5
5
5
24 h
CH2Cl2
O
O
18A
O
18A
18B
C
no decomposition
traces
Me
Me
Me
N
Ru
+
N
N
+
OMe
OMe
OMe
5
5
5
CH2Cl2
O
O
O
Z
15
18A
18B
Scheme 3.
dienic amides 25 and 26 were isolated in similar yields
(40%) with a (E,E)/(E,Z) ratio of 9/1 and 5/1, respectively
(Table 2, entries 12 and 13). Finally, when the (Z)-1,4-
dichlorobut-2-ene was utilized in the CM with 16, diene
27 was isolated in 57% yield with an (E,E)-27/(E,Z)-27
ratio of 16/1 (Table 2, entry 14).
O
OAc
[Ru]-III
O
Ru
Scheme 4.
observed as the desired cross-metathesis products of type A
were isolated in moderate to good yields with no trace of
mono-olefin of type B (Table 2, entries 11–14). Indeed,
when a reaction mixture consisting of camphorsultamide
16, oct-1-ene (5 equiv.), and catalyst [Ru]-III (10 mol%)
was stirred in CH2Cl2 at rt for 24 h, the cross-metathesis
product 24 was isolated in 61% yield with a 10/1 (E,E)-
24/(E,Z)-24 ratio (Table 2, entry 11). When the 1-acet-
oxy-but-3-ene and the (Z)-1,4-diacetoxybut-2-ene were
involved in the CM reaction with camphorsultamide 16,
4. Conclusion
Cross-metathesis reactions between dienic amides and a
variety of olefins turned out to be highly chemoselective at
the c,d-double bond producing mostly the corresponding
dienes of type A. When a mixture of diene of type A and
mono-olefin of type B is obtained, a decrease in the
amount of catalyst and/or the reaction time can result in
higher chemoselectivity in favor of A. This method allows

L. Ferrie´ et al. / Journal of Organometallic Chemistry 691 (2006) 5456–5465
5461
the formation of functionalized dienic amides under mild
conditions. As the Weinreb amides 18–23 can be trans-
formed into aldehydes, ketones or carboxylic acids and
as the optically active amides 24–27 can be involved in dia-
stereoselective reactions, the CM reaction of dienic amides
provides a valuable alternative for the preparation of use-
ful intermediates.
22.4, 13.9; Mass (EI) m/z: 196 (M+Å, 18), 165 (M ꢀ OMe+,
16), 111 (M ꢀ Hex+, 100), 81 (49).
5.2.2. Methyl (2E,4E)-6-(trimethylsilyl)hexa-2,4-dienoate
(7)
Purification on silica gel (Et2O/Petroleum Ether: 5/95 to
10/90) afforded 7 in 71% yield as a mixture of (E,E)-7/
(E,Z)-7 (5/1), contaminated by mono-olefin of type B (A/
B : 6/1).
5. Experimental
1
IR (neat): 1658, 1465, 1453 cmꢀ1; H NMR (400 MHz,
CDCl3) d: 7.27 (dd, J = 15.6, 11.0 Hz, 1H), 6.18 (dt,
J = 15.0 , 8.5 Hz, 1H), 6.04 (dd, J = 15.6, 11.0 Hz, 1H),
5.71 (d, J = 15.0 Hz, 1H), 3.73 (s, 3H), 1.68 (d,
J = 8.5 Hz, 2H), 0.02 (s, 9H); 13C NMR (100 MHz,
CDCl3) d: 168.1, 145.9, 143.0, 126.9, 116.5, 51.3, 25.2,
ꢀ1.9 (3C); Mass (EI) m/z: 198 (M+Å, 9), 167 (M ꢀ OMe+,
6), 73 (TMS+, 100), 66 (55).
5.1. General comments
Flash chromatography was performed with Merck
Geduran Si60 silica gel (40–63 UM). Infrared (IR) spectra
were recorded on a Bruker TENSORä 27 (IRFT), wave-
numbers are indicated in cmꢀ1 1H NMR spectra were
.
recorded on a Bruker AVANCE 400 at 400 MHz and data
are reported as follows: chemical shift in ppm from tetra-
methylsilane as an internal standard, multiplicity (s = sin-
glet, d = doublet, t = triplet, q = quartet, m = multiplet
or overlap of non-equivalent resonances), integration. 13C
NMR spectra were recorded on a Bruker AVANCE 400
at 100 MHz and data are reported as follows: chemical
shift in ppm from tetramethylsilane with the solvent as
an internal indicator (CDCl3 d: 77.0 ppm). Mass spectra
with electronic impact (MS-EI) were recorded from a Hew-
lett-Packard tandem 5890 A GC (12 m capillary column) –
5971 MS (70 eV). High resolution mass spectra (HRMS)
were performed by the Centre de Spectrochimie de l’Ecole
5.2.3. Methyl (2E,4E)-5-phenylpenta-2,4-dienoate (8)
Purification on silica gel (Et2O/Petroleum Ether: 5/95 to
10/90) afforded (E,E)-8 in 35% yield, contaminated by
methyl 7-phenylhexa-2,4,6-trienoate (A/triene: 4/1).
IR (neat): 1707, 1624, 1491, 1433 cmꢀ1 1H NMR
;
(400 MHz, CDCl3) d: 7.50–7.40 (m, 3H), 7.39–7.28 (m,
3H), 6.83–6.95 (m, 2H), 6.00 (d, J = 15.3 Hz, 1H), 3.77
(s, 3H); 13C NMR (100 MHz, CDCl3) d: 167.5, 144.8,
140.5, 135.9, 129.1, 128.8 (2C), 127.2 (2C), 126.1, 120.8,
51.5; Mass (EI) m/z: 188 (M+Å, 25), 157 (M ꢀ OMe+, 18),
129 (M ꢀ CO2Me+, 100), 128 (75), 77 (Ph+, 8); HRMS
(ESI): calculated for C12H12O2Na [M + Na]+: 211.0739,
found 211.0735.
´
Normale Superieure Ulm (Paris).
5.2. General procedure for CM reactions between methyl
sorbate and olefin cross-partners
5.2.4. Methyl (2E,4E)-6-(diethoxyphosphoryl)hexa-2,4-
dienoate (9)
Excess of diethyl allylphosphonate was removed from
the crude mixture under vacuum. Purification on silica
gel (AcOEt/Petroleum Ether: 20/80 to 100/0) afforded 9
in 56% yield as a mixture of (E,E)/(E,Z) stereoisomers in
a 5.5/1 ratio, along with mono-olefin of type B (A/B =
4/1), and contaminated by traces of methyl 8-(diethoxy-
phosphoryl)octa-2,4,6-trienoate detectable by GC/MS.
To a solution of methyl sorbate (150 mg, 1.2 mmol,
1 equiv.) and olefin partner (6 mmol, 5 equiv.) in CH2Cl2
(c = 0.1–0.2 M) was added the Grubbs–Hoveyda catalyst
[Ru]-III (18.5 mg, 0.030 mmol, 0.025 equiv.). After 24 h
stirring, another portion of Grubbs–Hoveyda catalyst
[Ru]-III was added (0.025 equiv.). After 24 h, silica was
added to the reaction mixture and after evaporation of
the solvent, the pad of silica was loaded on top of a silica
gel column and a flash chromatography purification was
achieved.
1
IR (neat): 3467, 1716, 1644, 1617, 1436 cmꢀ1; H NMR
(400 MHz, CDCl3) d: 7.27 (dd, J = 15.5, 11.0 Hz, 1H), 6.32
(ddd, J = 15.5, 11.0, 5.2 Hz, 1H), 6.07 (m, 1H), 5.86 (dd,
J = 15.5, 2.4 Hz, 1H), 4.11 (m, 4H), 3.74 (s, 3H), 2.72
(dd, J = 23.1, 7.6 Hz, 2H), 1.32 (t, J = 7.1 Hz, 6H); 13C
NMR (100 MHz, CDCl3) d: 167.2, 143.7, 132.6, 131.7,
120.7, 62.1, 51.5, 31.2, 16.4; Mass (EI) m/z: 262 (M+Å,
16), 247 (M ꢀ OMe+, 10), 124 (100), 109 (32); HRMS
(CI+, NH3): calculated for C11H20O5P [M + H]+:
263.1048, found 263.1044.
5.2.1. Methyl (2E,4E)-undeca-2,4-dienoate (6)
Purification on silica gel (Et2O/Petroleum Ether: 5/95 to
10/90) afforded 6 in 68% yield as a mixture of dienes (E,E)-
6/(E,Z)-6 (10/1), contaminated by the mono-olefin of type
B (A/B: 2.5/1).
1
IR (neat): 1724, 1656, 1436 cmꢀ1; H NMR (400 MHz,
CDCl3) d: 7.27 (dd, J = 15.4, 10.2 Hz, 1H), 6.22–6.08 (m,
2H), 5.78 (d, J = 15.4 Hz, 1H), 3.73 (s, 3H), 2.23–2.12
(m, 2H), 1.50–1.37 (m, 2H), 1.36–1.20 (m, 6H), 0.88 (t,
J = 7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3) d: 167.2,
149.9, 140.4, 138.7, 120.6, 51.3, 32.1, 31.4, 29.6, 28.7,
5.2.5. Methyl (2E,4E)-6-bromohexa-2,4-dienoate (10)
Purification on silica gel (AcOEt/Petroleum Ether: 2/98
to 5/95) afforded 10 in 48% yield as a mixture of (E,E)/
(E/Z) stereoisomers in a 32/1 ratio, contaminated by
methyl 8-bromoocta-2,4,6-trienoate (A/Triene = 6/1).

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L. Ferrie´ et al. / Journal of Organometallic Chemistry 691 (2006) 5456–5465
IR (neat): 1713, 1643, 1614, 1434, cmꢀ1
;
1H NMR
5.3. General procedure for CM reactions with dienic amides
(400 MHz, CDCl3) d: 7.19 (dd, J = 15.4, 11.0 Hz, 1H),
6.32 (dd, J = 15.0, 11.0 Hz, 1H), 6.18 (dt, J = 15.0,
7.5 Hz, 1H), 5.87 (d, J = 15.4 Hz, 1H), 3.97 (d,
J = 7.5 Hz, 2H), 3.69 (s, 3H); 13C NMR (100 MHz,
CDCl3) d: 166.9, 142.8, 136.7, 131.9, 122.8, 51.8, 31.2;
Mass (EI) m/z: 206 (M+Å 81Br, 15), 204 (M+Å 79Br, 15),
175 (M 81Br ꢀ OMe+, 15) , 173 (M 79Br ꢀ OMe+, 15),
125 (100), 93 (57), 66 (50).
To a solution of sorbamide (1 mmol, 1 equiv.) and the
olefin partner (5 mmol, 5 equiv.) in CH2Cl2 (c = 0.1–
0.2 M) was added Grubbs–Hoveyda catalyst [Ru]-III
(64 mg, 0.10 mmol, 0.1 equiv.). The solution was stirred
for 24 h and silica was then added to the reaction mixture.
After evaporation of the solvent, the pad of silica was
loaded on top of a silica gel column and a flash chromatog-
raphy purification was achieved.
5.2.6. Methyl (2E,4E)-6-(4-methylphenylsulfonamido)-
hexa-2,4-dienoate (11)
5.3.1. (2E,4E)-N,N-Diisopropylundeca-2,4-dienamide (17)
Purification on silica gel (AcOEt/Petroleum Ether: 15/85
to 20/80) afforded 17 in 36% yield as a mixture of the dienes
(E,E)-17/(E,Z)-17 (28/1).
Purification on silica gel (AcOEt/Hexanes: 5/95 to 40/
60) afforded 11 in 45% yield as a mixture of (E,E)/(E,Z)
stereoisomers in a 11.5/1 ratio, contaminated by mono-
olefin of type B (A/B = 4/1) and also by traces of p-
toluenesulfonamide.
1
IR (neat): 1659, 1630, 1606, 1460, 1411, 1376 cmꢀ1; H
NMR (400 MHz, CDCl3) d: 7.19 (dd, J = 14.6, 10.5 Hz,
1H), 6.09 (d, J = 14.6 Hz, 1H), 6.07 (dd, J = 15.2,
10.5 Hz, 1H), 6.02 (dt, J = 15.2, 6.9 Hz, 1H), 4.02 (m,
1H), 3.79 (m, 1H), 2.14 (qapp, J = 7.0 Hz, 2H), 1.50–1.10
(m, 20H), 0.88 (t, J = 7.0 Hz, 3H); 13C NMR (100 MHz,
CDCl3) d: 166.5, 142.1, 141.7, 128.9, 121.3, 47.6 (br), 45.8
(br), 32.9, 31.6, 28.8 (2C), 22.6, 21.5 (2C, br), 20.8 (2C,
br), 14.1; Mass (EI) m/z: 265 (M+Å, 36), 250 (M ꢀ Me+,
13), 222 (M ꢀ Pr+, 26), 208 (M ꢀ Bu+ 22), 194
(M ꢀ Pent+, 9), 180 (M ꢀ Hex+, 36), 165 (M ꢀ NiPrþ2 ,
100), 100 (NiPrþ2 , 54), 95 (95), 81 (61).
IR (neat): 3238, 1694, 1650, 1620, 1597, 1438 cmꢀ1; H
1
NMR (400 MHz, CDCl3) d: 7.66 (d, J = 8.3 Hz, 2H),
7.21 (d, J = 8.3 Hz, 2H), 7.03 (dd, J = 15.4, 11.0 Hz, 1H),
6.12 (dd, J = 15.2, 11.1 Hz, 1H), 5.82 (dt, J = 15.2,
5.5 Hz, 1H), 5.68 (d, J = 15.4 Hz, 1H), 5.36 (br s, NH),
3.63 (s, 3H), 3.58 (m, 2H), 2.32 (s, 3H); 13C NMR
(100 MHz, CDCl3) d: 167.3, 143.5, 143.3, 139.4, 136.9,
129.9 (2C), 127.1 (2C), 126.3, 121.4, 51.6, 44.6, 21.5; Mass
(EI) m/z: 295 (M+Å, 1), 264 (M ꢀ OMe+, 5), 155 (19), 140
(44), 111 (100), 108 (84), 91 (77), 80 (61); HRMS (CI+,
NH3): calculated for C14H21N2O4S [M + NH4]+:
313.1222, found 313.1216.
5.3.2. (2E,4E)-N-Methoxy,N-methylundeca-2,4-dienamide
(18)
5.2.7. Methyl (2E,4E)-6-oxohepta-2,4-dienoate (12)
Purification on silica gel (AcOEt/Hexanes: 3/97 to 20/80)
afforded (E,E)-12 as a single stereoisomer in 13% yield,
contaminated by dimethyl octa-2,4,6-trienedioate (A/Tri-
ene: 6/1).
Only 5 mol% of catalyst [Ru]-III were used and the reac-
tion was stopped after 1 h. Purification on silica gel
(AcOEt/Petroleum Ether: 20/80), afforded 18 in 64% yield
as a mixture of the dienes (E,E)-18/(E,Z)-18 (49/1), con-
taminated by mono-olefin of type B (A/B: 13/1). When
the reaction was stirred for 24 h, a 5/1 A/B ratio was
observed.
1
IR (neat): 1717, 1660, 1627, 1599, 1436 cmꢀ1; H NMR
(400 MHz, CDCl3) d: 7.27 (dd, J = 15.4, 11.5 Hz, 1H), 7.07
(dd, J = 15.5, 11.5 Hz, 1H), 6.36 (d, J = 15.5 Hz, 1H), 6.18
(d, J = 15.4 Hz, 1H), 3.72 (s, 3H), 2.26 (s, 1H); 13C NMR
(100 MHz, CDCl3) d: 197.8, 166.2, 141.5, 139.1, 136.3,
128.6, 52.0, 27.9; Mass (EI) m/z: 154 (M+Å, 46), 139
(M ꢀ Me+, 100), 123 (M ꢀ OMe+, 20), 111 (76), 95 (37).
1
IR (neat): 1659, 1630, 1606, 1460, 1411, 1376 cmꢀ1; H
NMR (400 MHz, CDCl3) d: 7.31 (dd, J = 15.2, 10.6 Hz,
1H), 6.37 (d, J = 15.2 Hz, 1H), 6.23 (dd, J = 15.1,
10.7 Hz, 1H), 6.12 (dt, J = 15.1, 6.5 Hz, 1H), 3.70 (s,
3H), 3.25 (s, 3H), 2.16 (qapp, J = 7.0 Hz, 2H), 1.50–1.37
(m, 2H), 1.36–1.20 (m, 6H), 0.88 (t, J = 7.0 Hz, 3H); 13C
NMR (100 MHz, CDCl3) d: 167.5, 144.1, 144.0, 128.7,
116.8, 61.7, 33.0, 32.5, 31.6, 28.9, 28.7, 22.6, 14.1; Mass
(EI) m/z: 225 (M+Å, 2), 165 (M+Å ꢀ N(OMe)Me, 100), 81
(85); HRMS (ESI): calculated for C13H23NO2Na
[M + Na]+: 248.1634, found 248.1626.
5.2.8. tert-Butyl methyl (2E,4E)-hexa-2,4-dienoate (13)
Purification on silica gel (AcOEt/Hexanes: 0/100 to
3/97) afforded 13 in 30% yield as a mixture of (E,E)/
(E/Z) stereoisomers in a 50/1 ratio, contaminated by
methyl 7-phenyl-hexa-2,4,6-trienoate (A/Triene: 9/1).
IR (neat): 1699, 1609 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d: 7.24 (dd, J = 15.0, 11.5 Hz, 1H), 7.14 (dd, J = 14.8,
11.5 Hz, 1H), 6.10 (d, J = 15.0 Hz, 1H), 6.06 (d,
J = 14.8 Hz, 1H), 3.71 (s, 3H), 1.43 (s, 9H); 13C NMR
(100 MHz, CDCl3) d: 166.5, 165.2, 141.3, 139.7, 130.6,
127.3, 81.2, 51.9, 28.1 (3C); Mass (EI) m/z: 213 (M + H+,
1), 212 (M+Å, 1), 181 (M ꢀ OMe+, 20), 157 (100), 139
(M ꢀ OtBu+, 77), 111 (54), 57 (67); HRMS (CI+, NH3): cal-
culated for C11H17O4 [M + H]+: 213.1127, found 213.1121.
5.3.3. (2E,4E)-6-Bromo-N-methoxy,N-methylhexa-2,4-
dienamide (19)
Purification on silica gel (AcOEt/Petroleum Ether: 10/90
to 20/80) afforded 19 in 39% yield as a mixture of (E,E)/
(E,Z) stereoisomers in a 19/1 ratio.
1
IR (neat): 1655, 1625, 1605, 1414, 1380 cmꢀ1; H NMR
(400 MHz, CDCl3) d: 7.30 (dd, J = 15.2, 11.0 Hz, 1H), 6.54
(d, J = 15.2 Hz, 1H), 6.46 (dd, J = 15.0, 11.0 Hz, 1H), 6.24

L. Ferrie´ et al. / Journal of Organometallic Chemistry 691 (2006) 5456–5465
5463
(dt, J = 15.0, 7.8 Hz, 1H), 4.05 (d, J = 7.8 Hz, 1H), 3.71 (s,
3H), 3.26 (s, 3H); 13C NMR (100 MHz, CDCl3) d: 166.5,
141.3, 135.8, 132.7, 121.0, 61.9, 32.4, 31.7; Mass (EI) m/z:
235 (M+Å 81Br, 7), 233 (M+Å 79Br, 8), 176 (7), 175 (M+Å
81Br ꢀ N(OMe)Me, 99), 173 (M+Å 79Br ꢀ N(OMe)Me,
100), 154 (64), 94 (63), 66 (79); HRMS (CI+, NH3): calcu-
lated for C8H1379BrNO2 [M + H]+: 234.0130, found
234.0134, calculated for C8H1381BrNO2 [M + H]+:
236.0110, found 236.0114.
10.5 Hz, 1H), 3.70 (s, 3H), 3.24 (s, 3H), 1.67 (d,
J = 7.9 Hz, 2H), 0.02 (s, 9H); 13C NMR (100 MHz,
CDCl3) d 167.9, 144.5, 142.0, 127.4, 114.7, 61.7, 32.5,
25.1, ꢀ1.9 (3C); Minor isomer (E,Z)-22: 1H NMR
(400 MHz, CDCl3) d 7.31 (dd, J = 15.0, 11.6 Hz, 1H),
6.42 (d, J = 15.0 Hz, 1H), 6.12 (dd, J = 11.6, 10.8 Hz,
1H), 6.09 (dt, J = 10.8, 9.2, 1H), 3.71 (s, 3H), 3.25 (s,
3H), 1.85 (dd, J = 9.2, 1.2 Hz, 2H), 0.02 (s, 9H); 13C
NMR (100 MHz, CDCl3) d 167.7, 138.7, 138.3, 124.7,
117.3, 61.7, 32.4, 21.0, ꢀ1.8 (3C); Mass (EI) m/z: 227
(M+Å, 7), 212 (M ꢀ Me+, 2), 196 (M ꢀ OMe+, 2), 180 (1),
167 (M+Å ꢀ N(OMe)Me, 34), 151 (44), 109 (2), 73
(TMS+, 100), 66 (9), 59 (5); HRMS (ESI): calculated for
C11H21NO2SiNa [M + Na]+: 250.1247, found 250.1239.
5.3.4. (2E,4E)-N-Methoxy,N-methyl-6-chlorohexa-2,4-
dienamide (20)
Only 5 mol% of catalyst [Ru]-III were used and the reac-
tion was stopped after 30 min. Purification on silica gel
(AcOEt/Petroleum Ether: 20/80) afforded 20 in 59% yield
as a mixture of the dienes (E,E)-20/(E,Z)-20 (32/1), con-
taminated by the mono-olefin of type B (A/B: 13/1). When
the reaction was stirred for 24 h with 10 mol% of catalyst
[Ru]-III a 2/1 A/B ratio was observed.
5.3.7. (2E,4E)-N-Methoxy,N-methyl-6-acetoxyhexa-2,4-
dienamide (23)
Purification on silica gel (AcOEt/Petroleum Ether: 35/
65) afforded 23 in 42% yield as a mixture of the dienes
(E,E)-23/(E,Z)-23 (5/1).
1
IR (neat): 1656, 1628, 1606, 1413, 1378 cmꢀ1; H NMR
1
(400 MHz, CDCl3) d: 7.26 (dd, J = 15.2, 11.0 Hz, 1H), 6.49
(d, J = 15.4 Hz, 1H), 6.44 (dd, J = 15.0, 11.0 Hz, 1H), 6.12
(dt, J = 15.0, 6.9 Hz, 1H), 4.10 (dd, J = 6.9, 1.0 Hz, 2H),
3.66 (s, 3H), 3.21 (s, 3H); 13C NMR (100 MHz, CDCl3)
d: 166.4, 141.3, 135.4, 131.9, 120.7, 61.7, 44.0, 32.3; Mass
(EI) m/z: 191 (M+Å 37Cl, 2), 189 (M+Å 35Cl, 6), 154
(M ꢀ Cl+, 20), 131 (M+Å 37Cl ꢀ N(OMe)Me, 34), 129
(M+Å 35Cl ꢀ N(OMe)Me, 100); HRMS (ESI): calculated
for C8H13NO235Cl [M + H]+: 190.0638, found 190.0635.
IR (neat): 1737, 1659, 1632, 1607, 1417, 1380 cmꢀ1; H
NMR (400 MHz, CDCl3) d 7.29 (dd, J = 15.2, 11.2 Hz,
1H), 6.51 (d, J = 15.2 Hz, 1H), 6.24 (dd, J = 15.3,
11.0 Hz, 1H), 6.11 (dt, J = 15.3, 5.8 Hz, 1H), 4.65 (d,
J = 5.8 Hz, 2H), 3.70 (s, 3H), 3.24 (s, 3H), 2.08 (s, 3H);
13C NMR (100 MHz, CDCl3) d 170.2, 166.3, 141.5,
134.1, 130.8, 119.9, 63.5, 61.5, 32.0, 20.5; Mass (EI) m/z:
213 (M+Å, 4), 153 (M+Å ꢀ N(OMe)Me, 20), 111 (100);
HRMS (ESI): calculated for C10H16NO4 [M + H+]:
214.1079, found 214.1055.
5.3.5. (2E,4E)-N-Methoxy,N-methyl-7-acetoxyhepta-2,4-
dienamide (21)
5.3.8. N-[(2E,4E)-Undeca-2,4-dienoyl]-(S)-2,10-
camphorsultam (24)
Purification on silica gel (AcOEt/Petroleum Ether: 35/
65), afforded 21 in 46% yield as a mixture of the dienes
(E,E)-21/(E,Z)-21 (7/1), contaminated by mono-olefin of
type B (A/B: 24/1).
Purification on silica gel (AcOEt/Petroleum Ether: 10/
90) afforded 24 in 61% yield as a mixture of the dienes
(E,E)-24/(E,Z)-24 (10/1).
20
1
IR (neat): 1735, 1655, 1628, 1605, 1414, 1379 cmꢀ1; H
M.p. 84–86 °C; ½aꢁD þ 64:4 (c 0.56, CHCl3); IR (neat):
1
NMR (400 MHz, CDCl3) d: 7.24 (dd, J = 15.2, 11.0 Hz,
1H), 6.38 (d, J = 15.2 Hz, 1H), 6.26 (dd, J = 15.3,
11.2 Hz, 1H), 6.02 (dt, J = 15.3, 7.0 Hz, 1H), 4.04 (t,
1682, 1638, 1607, 1456, 1412, 1392, 1328, 1271 cmꢀ1; H
NMR (400 MHz, CDCl3) d 7.35 (dd, J = 14.8, 10.0 Hz,
1H), 6.51 (d, J = 14.8 Hz, 1H), 6.24 (dd, J = 15.2,
10.0 Hz, 1H), 6.17 (dt, J = 15.2, 6.2 Hz, 1H), 3.93 (dd,
J = 7.5, 5.1 Hz, 1H), 3.50 (d, J = 13.8 Hz, 1H), 3.46 (d,
J = 13.8 Hz, 1H), 2.16 (qapp, J = 6.5 Hz, 2H), 2.16–2.04
(m, 2H), 1.96–1.84 (m, 3H), 1.60–2.40 (m, 10H), 1.16 (s,
3H), 0.96 (s, 3H), 0.85 (m, 3H); 13C NMR (100 MHz,
CDCl3) d 164.5, 146.6, 146.1, 128.6, 118.3, 65.1, 53.1,
48.4, 47.7, 44.6, 38.5, 33.0, 32.8, 31.6, 28.8, 28.5, 26.5,
22.5, 20.8, 19.8, 14.0; Mass (EI) m/z: 379 (M+Å, 12), 294
(M ꢀ Hex+, 28), 165 (M ꢀ CO ꢀ Sultam+, 100); HRMS
(CI+, CH4): calculated for C21H34NSO3 [M + H]+:
380.2259, found 380.2253.
J = 6.7 Hz, 2H), 3.66 (s, 3H), 3.20 (s, 3H), 2.46 (qapp
,
J = 6.7 Hz, 2H), 2.00 (s, 3H); 13C NMR (100 MHz,
CDCl3) d: 170.7, 166.8, 142.7, 137.6, 130.8, 118.0, 62.8,
61.5, 32.1, 31.9, 20.6; Mass (EI) m/z: 227 (M+Å, 8), 184
(M ꢀ Ac+, 1), 167 (M+Å ꢀ N(OMe)Me, 15), 107 (100);
HRMS (ESI): calculated for C11H18NO4 [M + H]+:
228.1240, found 228.1236.
5.3.6. (2E,4E)-N-Methoxy,N-methyl-6-(trimethylsilyl)-
hexa-2,4-dienamide (22)
Purification on silica gel (AcOEt/Petroleum Ether: 20/
80) afforded (E,E)-22 in 37% yield and (E,Z)-22 in 8%
yield ((E,E)/(E,Z): 4/1).
5.3.9. N-[(2E,4E)-7-Acetoxyhepta-2,4-dienoyl]-(S)-2,10-
camphorsultam (25)
Purification on silica gel (AcOEt/Petroleum Ether: 15/
85) afforded 25 in 40% yield as a mixture of the dienes
(E,E)-25/(E,Z)-25 (9/1).
IR (neat): 1664, 1640, 1621, 1462, 1416, 1381 cmꢀ1
;
1
Major isomer (E,E)-22: H NMR (400 MHz, CDCl3) d:
7.31 (dd, J = 15.1, 10.5 Hz, 1H), 6.29 (d, J = 15.4 Hz,
1H), 6.17 (dt, J = 14.9, 8.0 Hz, 1H), 6.09 (dd, J = 14.9,

5464
L. Ferrie´ et al. / Journal of Organometallic Chemistry 691 (2006) 5456–5465
20
½aꢁD þ 82:1 (c 0.39, CHCl3); IR (neat): 1735, 1676, 1634,
for financial support of this work. We also wish to
acknowledge Dr. Fisher and Dr. Trimmer from Materia
(USA) for a generous gift of the Grubbs–Hoveyda
catalyst.
1606, 1456, 1413, 1326, 1271 cmꢀ1; H NMR (400 MHz,
1
CDCl3) d 7.29 (dd, J = 14.8, 11.0 Hz, 1H), 6.51 (d,
J = 14.8 Hz, 1H), 6.5 (dd, J = 15.2, 11.0 Hz, 1H), 6.15
(dt, J = 15.2, 7.0 Hz, 1H), 4.08 (t, J = 6.5 Hz, 2H), 3.88
(dd, J = 7.4, 5.2 Hz, 1H), 3.47 (d, J = 13.8 Hz, 1H), 3.39
(d, J = 13.8 Hz, 1H), 2.45 (qapp, J = 6.5 Hz, 2H), 2.12–
2.02 (m, 2H), 1.98 (s, 3H) 1.92–1.77 (m, 3H), 1.37 (m,
1H), 1.30 ( m, 1H), 1.11 (s, 3H), 0.92 (s, 3H); 13C NMR
(100 MHz, CDCl3) d 170.3, 163.8, 143.7, 136.6, 130.1,
121.4, 65.0, 63.4, 52.9, 48.3, 47.6, 44.5, 38.3, 32.6, 32.1,
26.3, 20.8, 20.7, 19.7; Mass (EI) m/z: 381 (M+Å, 1), 338
(M ꢀ Ac+, 1), 135 (M ꢀ AcOH ꢀ Sultam+, 11), 107
(100); HRMS (CI+, CH4): calculated for C19H28NO5S
[M + H]+: 382.1688, found 382.1682.
References
[1] (a) For recent reviews, see: M. Schuster, S. Blechert, Angew. Chem.
Int. Ed. Engl. 36 (1997) 2067;
(b) R.H. Grubbs, S. Chang, Tetrahedron 54 (1998) 4413;
(c) S.K. Armstrong, J. Chem. Soc. Perkin Trans. 1 (1998) 371;
(d) A.J. Phillips, A.D. Abell, Aldrichimica Acta 32 (1999) 75;
(e) S. Blechert, Pure Appl. Chem. 71 (1999) 1393;
(f) A. Furstner, Angew. Chem. Int. Ed. 39 (2000) 3013;
¨
(g) T.M. Trnka, R.H. Grubbs, Acc. Chem. Res. 34 (2001) 18;
(h) R.H. Grubbs, Handbook of Metathesis, Wiley-VCH, Weinheim,
2003.
[2] For a recent review on Olefin cross-metathesis, see: S.J. Connon, S.
Blechert, Angew. Chem. Int. Ed. 42 (2003) 1900.
[3] (a) R.R. Schrock, J.S. Murdzek, G.C. Bazan, J. Robbins, M. Dimare,
M. O’Regan, J. Am. Chem. Soc. 112 (1990) 3875;
(b) G.C. Bazan, E. Khosravi, R.R. Schrock, W.J. Feast, V.C.
Gibson, M.B. O’Regan, J.K. Thomas, W.M. Davis, J. Am. Chem.
Soc. 112 (1990) 8378;
(c) G.C. Bazan, J.H. Oskam, H.N. Cho, L.Y. Park, R.R. Schrock, J.
Am. Chem. Soc. 113 (1991) 6899.
[4] P. Schwab, M.B. France, J.W. Ziller, R.H. Grubbs, Angew. Chem.
Int. Ed. Engl. 34 (1995) 2039.
[5] M. Scholl, S. Ding, C.W. Lee, R.H. Grubbs, Org. Lett. 1 (1999)
953.
[6] J.S. Kingbury, J.P.A. Harrity, P.J. Bonitatebus Jr., A.H. Hoveyda, J.
Am. Chem. Soc. 122 (2000) 8168.
[7] K.C. Nicolaou, P.G. Bulger, D. Sarlah, Angew. Chem. Int. Ed. 44
(2005) 4490, and references therein.
[8] (a) For examples, see: K.C. Nicolaou, M.H.D. Posterma, E.W. Yue,
A. Nadin, J. Am. Chem. Soc. 118 (1996) 10335;
(b) L.M.M. Cabrejas, S. Rohrbach, D. Wagner, J. Kallen, G. Zenke,
J. Wagner, Angew. Chem. Int. Ed. 38 (1999) 2443;
(c) C.A. Dvorak, W.D. Schmitz, D.J. Poon, D.C. Pryde, J.P. Lawson,
R.A. Amos, A.I. Meyers, Angew. Chem. Int. Ed. 39 (2000) 1664;
(d) R.M. Garbaccio, S.J. Stachel, D.K. Baeschlin, S.J. Danishefsky,
J. Am. Chem. Soc. 123 (2001) 10903;
5.3.10. N-[(2E,4E)-6-Acetoxyhexa-2,4-dienoyl]-(S)-2,10-
camphorsultam (26)
Purification on silica gel (AcOEt/Petroleum Ether: 15/
85) afforded 26 in 40% yield as a mixture of the dienes
(E,E)-26/(E,Z)-26 (5/1).
20
½aꢁD þ 44:9 (c 0.90, CHCl3); IR (neat, cmꢀ1): 1738, 1676,
1
1639, 1609, 1455, 1413, 1374, 1327, 1270 cmꢀ1; H NMR
(400 MHz, CDCl3) d 7.32 (dd, J = 14.8, 11.1 Hz, 1H),
6.62 (d, J = 14.8 Hz, 1H), 6.43 (dd, J = 15.3, 11.2 Hz,
1H), 6.15 (dt, J = 15.3, 5.50 Hz, 1H), 4.65 (d, J = 5.5 Hz,
2H), 3.91 (dd, J = 7.4, 5.2 Hz, 1H), 3.49 (d, J = 13.8 Hz,
1H), 3.42 (d, J = 13.8 Hz, 1H), 2.16–2.04 (m, 2H), 2.06
(s, 3H) 1.96–1.80 (m, 3H), 1.40 (m, 1H), 1.33 (m, 1H),
1.13 (s, 3H), 0.94 (s, 3H); 13C NMR (100 MHz, CDCl3) d
170.3, 163.8, 143.7, 136.6, 130.1, 121.4, 65.0, 63.4, 52.9,
48.3, 47.6, 44.5, 38.3, 32.6, 26.3, 20.7 (2C), 19.7; HRMS
(CI+, CH4): calculated for C18H26NO5S [M + H]+:
368.1532, found 368.1536.
5.3.11. N-[(2E,4E)-6-Chloro-hexa-2,4-dienoyl]-(S)-2,10-
camphorsultam (27)
(e) K. Basu, J.C. Eppich, L.A. Paquette, Adv. Synth. Catal. 344
(2002) 615;
(f) K. Biswas, H. Lin, J.T. Njardarson, M.D. Chappell, T.-C. Chou,
Y. Guan, W.P. Tong, L. He, S.B. Horwitz, S.J. Danishefsky, J. Am.
Chem. Soc. 124 (2002) 9825;
Purification on silica gel (AcOEt/Petroleum Ether: 10/
90) afforded 27 in 57% yield as a mixture of the dienes
(E,E)-27/(E,Z)-27 (16/1).
20
½aꢁD þ 81:1 (c 0.54, CHCl3); IR (neat): 1675, 1634, 1607,
(g) K. Yamamoto, K. Biswas, C. Gaul, S.J. Danishefsky, Tetrahedron
Lett. 44 (2003) 3297.
1
1456, 1413, 1373, 1328, 1271 cmꢀ1; H NMR (400 MHz,
[9] (a) S. Randl, N. Lucas, S.J. Connon, S. Blechert, Adv. Synth. Catal.
344 (2002) 631;
CDCl3) d 7.34 (dd, J = 14.8, 11.1 Hz, 1H), 6.70 (d,
J = 14.8 Hz, 1H), 6.17 (dd, J = 14.9, 11.1 Hz, 1H), 6.09
(dt, J = 14.9, 6.9 Hz, 1H), 4.13 (d, J = 6.9 Hz, 2H), 3.92
(dd, J = 7.4, 5.3 Hz, 1H), 3.50 (d, J = 13.8 Hz, 1H), 3.43
(d, J = 13.8 Hz, 1H), 2.16–2.04 (m, 2H), 1.96–1.80 (m,
3H), 1.41 (m, 1H), 1.34 (m, 1H), 1.15 (s, 3H), 0.95 (s,
3H); 13C NMR (100 MHz, CDCl3) d 163.7, 143.2, 137.5,
131.3, 122.1, 65.0, 53.0, 48.4, 47.7, 44.6, 43.7, 38.3, 32.7,
26.4, 20.7, 19.8;. HRMS (CI+, CH4): calculated for
C16H23NO3S35Cl [M + H]+: 344.1087, found 344.1093.
(b) R.R. Cesati III, J. de Armas, A.H. Hoveyda, J. Am. Chem. Soc.
126 (2003) 96;
(c) H.Y. Lee, B.G. Kim, M.L. Snapper, Org. Lett. 5 (2003) 1855;
(d) F. Royer, C. Vilain, L. Elka¨ım, L. Grimaud, Org. Lett. 5 (2003)
2007;
(e) H.-Y. Lee, H.Y. Kim, H. Tae, B.G. Kim, J. Lee, Org. Lett. 5
(2003) 3439;
(f) P. Dewi, S. Randl, S. Blechert, Tetrahedron Lett. 46 (2005)
577.
[10] T.W. Funk, J. Efskind, R.H. Grubbs, Org. Lett. 7 (2005) 187.
[11] (a) J. Cossy, S. BouzBouz, A.H. Hoveyda, J. Organomet. Chem. 634
(2001) 216;
Acknowledgements
(b) S. Randle, S. Gessler, H. Wakamatsu, S. Blechert, Chem.
Commun. (2001) 1692;
One of us (L.F.) thanks the MRES for a grant. D.A.
(c) S. Randle, S.J. Connon, S. Blechert, Chem. Commun. (2001)
1796.
´ ´
´
thanks the Societe de Chimie Therapeutique/SERVIER

L. Ferrie´ et al. / Journal of Organometallic Chemistry 691 (2006) 5456–5465
5465
[12] Traces of a trienic compound were observed by GC/MS and 1H
NMR along with dienic esters 8, 9, 10, 12 and 13 (see experimental
section).
[13] T.-L. Choi, A.K. Chatterjee, R.H. Grubbs, Angew. Chem. Int. Ed.
40 (2001) 1277.
(c) W. Oppolzer, G. Poli, A.J. Kingma, C. Starkemann, G. Bernar-
dinelli, Helv. Chim. Acta 70 (1987) 2201.
[15] The experiences were carried out in the presence of a known quantity
of dodecane as an internal standard of calibration and were followed
by GC/MS.
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¨
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(b) S.V. Ley, L.R. Cox, G. Meek, K.-H. Metten, C. Pique´, J.M.
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