Iridium-catalyzed hydroiodination of functionalized alkynes

Article abstract of DOI:10.1016/j.jorganchem.2010.10.052

The efficiency of an Ir(I)/HI system has been studied. The association of hydroiodic acid with iridium has been tested in the catalytic hydroiodination of alkynes. The use of [Ir(cod)Cl]₂ dimer led to clean hydroiodination reactions and afforde

Full text of DOI:10.1016/j.jorganchem.2010.10.052

Journal of Organometallic Chemistry 696 (2011) 433e441
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Iridium-catalyzed hydroiodination of functionalized alkynes
,
a,
*
Mehdi Ez-Zoubir a, Jack A. Brown b, Virginie Ratovelomanana-Vidal a , Véronique Michelet
*
a Laboratoire Charles Friedel, Ecole Nationale Supérieure de Chimie de Paris Chimie ParisTech UMR 7223, 11 rue P. et M. Curie, F-75231 Paris Cedex 05, France
b Epinova DPU, II CEDD, GlaxoSmithKline, Medicines Research Centre, Gunnels Wood Road, Stevenage, SG1 2NY, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
The efficiency of an Ir(I)/HI system has been studied. The association of hydroiodic acid with iridium has
been tested in the catalytic hydroiodination of alkynes. The use of [Ir(cod)Cl]2 dimer led to clean
hydroiodination reactions and afforded the corresponding vinyliodides as a mixture of derivatives, where
the Markovnikov type adduct was found to be the major product (80/20 to 93/7 ratio), in good yields. The
mechanism was investigated and two main pathways seemed to be involved, one based on an initial
Received 10 September 2010
Received in revised form
20 October 2010
Accepted 22 October 2010
Available online 30 October 2010
oxidative addition of HI to the Ir(I) complex and the other one based on a
p-activation of the alkyne
moiety. The corresponding vinyliodides were engaged in Pd-catalyzed cross-coupling (Sonogashira and
SuzukieMiyaura) reactions under organoaqueuous conditions.
Ó 2010 Elsevier B.V. All rights reserved.
Keywords:
Iridium
Alkynes
Catalysis
Hydroiodination
Enynes
Cross-coupling reactions
1. Introduction
on an iodoarylation reaction of arylacetylenes was recently described
[12]. The use of molecular iodine [13] in the presence of various acidic
The emergence of cross-coupling reactions including Mizoroki-
Heck [1], Sonogashira [2] and SuzukieMiyaura [3] reactions has made
the vinyliodide derivatives highly valuable substrates, however their
preparation starting from alkynes [4] has been particularly chal-
lenging. Historically, various boron halides or metal hydrides in the
presence of an iodine source have been used to avoid the use of
gaseous hydrogen iodide and to increase the scope of this trans-
formation: haloboration [5], hydroboration, hydrostannylation,
hydrozincation or hydrozirconation or hydroindation/I2 reactions [6]
may be cited as seminalexamples. Based on Kishi’s report [7], a recent
example of cuprosilylation followed by NIS (N-iodosuccinimide)
trapping allowed the formation of functionalized vinyliodides [8].
Selective conditions employing LiI/AcOH or TMSCl/NaI/H2O systems
were found to be efficient for the hydroiodination of propargylic or
homopropargylic alcohols and alkylsubstituted alkynes and inter-
estingly led to the Markovnikov adduct [9]. In the case of activated
alkynes such as ynones,1-alkynoic acids or derivatives, these systems
affordedtheanti-Markovnikoviodoalkenes[10].Theuseofzinciodide
and tert-butyl iodidewas necessary to promote the mild and selective
hydrohalogenationof3-propynamides[11].Anelegantstrategybased
additives such as g-alumina, titanium tetraiodide led in most cases to
the alkenyl or alkanyl diiodide [14], whereas the association of I2 with
hydrophosphane afforded the desired iodoalkenes in excellent
selectivity [15]. To the best of our knowledge, the groups of Campos,
Rodriguez and Mitchenko described unique catalytic systems based
on eithera mixture of iodine, CuO.HBF4 (50mol%)andtriethylsilaneor
aplatinum(IV) catalyst[16,17]. Mitchenko, Beletskayaand co-workers
reported the Pt-catalyzed dimerization of acetylene, which was
accompanied by addition of iodine and which led to (E, E)-1,4-diio-
dobuta-1,3-diene [18]. The preparation of vinyliodides still requires
investigationforfunctionalizedsubstrates, whicharenon-compatible
with the classical methods. In the course of our study of alkyne and
enyne dimerization reactions in the presence of [Ir2H2I3((rac)-
Binap)2]þIꢀ [19], we observed the formation of an alkenyliodide
resulting from the hydroiodination of the alkynyl moiety. We there-
fore decided to investigate the possibility of finding a suitable catalyst
for the formation of vinyliodide derivatives and wish to present our
preliminary results herein.
2. Results and discussion
2.1. Optimization of the catalytic system
* Corresponding authors.
E-mail addresses: virginie-vidal@chimie-paristech.fr (V. Ratovelomanana-Vidal),
veronique-michelet@chimie-paristech.fr (V. Michelet).
Initial efforts have focused on the optimization of an efficient
system using dimethyl 2-(prop-2-ynyl)propanedioate 1 as a model
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.10.052

434
M. Ez-Zoubir et al. / Journal of Organometallic Chemistry 696 (2011) 433e441
Table 1
[M] (8 mol%)
Ligand
I
HI (1.1 eq.)
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
I
+
toluene, 80 °C, 1h
1
2a
2b
.
Entry
[M] Catalyst
Ligand (16 mol%)
Conv (%)
2a/2b ratio (%)a
1
2
RuCl3
IrCl3
AuCl3
AuCl
PdCl2
PtCl2
[Rh(cod)Cl]2
[Ir(cod)Cl]2
/
[Ir(cod)Cl]2
[Ir(cod)Cl]2
[Ir(cod)Cl]2
[Ir(cod)Cl]2
[Ir(cod)Cl]2
[Ir(cod)Cl]2
/
/
/
/
/
/
/
/
32
23
8
15
89/11
>95/5
>95/5
>95/5
>95/5
3b
4b
5
35
,
d
6
7
99 (20e)
66
>95/5c
69/31
83/17
100/0
84/16
80/20
82/18
86/14
80/20
80/20
8
99 (72e)
20
9f
/
10g
11g
12g
13g
14g
15g
PPh3
PPh(Cy)2
P(Ph)2Cy
P(p-OMeeC6H4)3
P(p-CF3eC6H4)3
dppfh
99
99
99
99
99
99
a
Determined by 1H NMR spectroscopy.
b
c
Room temperature.
Degradation.
Z isomer (10%).
Isolated yield.
Dioxane.
d
e
f
g
h
19 h.
8 mol%.
substrate. We investigated the use of various organometallic
species at 80 ꢁC in toluene (Table 1). In all cases, the reaction
employing 8 mol% of catalyst and 1.1 eq. of aqueous hydroiodic acid
allowed the formation of iodides 2a (resulting from a Markovnikov
type [20] addition of HI on the triple bond) and 2b in various ratio,
2a and 2b being non-separable by column chromatography. The E
stereochemistry of 2b was determined by 1H NMR spectroscopy
considering the coupling constant of the vinylic protons.
an excellent reactivity (Table 1, entry 6), but led to several
unidentified by-products. The use of Rh(I) and Ir(I) catalysts led to
the best results (Table 1, entries 7e8), the mixture 2a/2b being
isolated in 72% yield in the case of the iridium dimer. The
importance of the catalyst was demonstrated by performing the
reaction without an organometallic species (Table 1, entry 9):
a low conversion was observed and the reaction favoured the
expected Markovnikov type adduct 2a. We therefore selected the
Ir(I) catalyst and studied the influence of phosphorous ligands on
the 2a/2b ratio (Table 1, entries 10e15). The introduction of an
Low conversions were observed with RuCl3, IrCl3, AuCl3, AuCl
and PdCl2 (Table 1, entries 1e5). Notably, PtCl2 as catalyst offered
Table 2
[Ir(cod)Cl]2 (4 mol%)
I
HI (1.1 eq.)
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
I
Solvent, 80 °C, 1h
+
1
2a
2b
.
Entry
Solvent
Conv (yielda) (%)
2a/2b ratio (%)b
1c
2
CH2Cl2
ClCH2CH2Cl
Et2O
MeOH
THF
99
99
50
99 (34)
99 (51)
99 (77)
85/15
87/13
100/0
95/5
95/5
93/7
3d
4
5
6
Dioxane
a
Isolated yield.
b
c
Determined by 1H NMR spectroscopy.
60 ꢁC.
40 ꢁC, 16 h.
d

M. Ez-Zoubir et al. / Journal of Organometallic Chemistry 696 (2011) 433e441
435
Table 3
[Ir(cod)Cl]2 (4 mol%)
HI (1.1 eq.)
I
+
R
R
R
I
toluene or dioxane
80 °C, 1 - 17 h
3-15
4-16b
4-16a
.
Entry
Alkyne
Solvent
Product
Time (h)
Yielda (%)
a/b ratio (%)b
Toluene
Dioxane
17
1
60
60
80/20
I
90/10c
EtO2C
EtO2C
EtO2C
EtO2C
I
+
EtO2C
Ph
1
EtO2C
Ph
Ph
4b
3
4a
Toluene
Dioxane
17
1
66
69
75/25
I
88/12c
EtO2C
EtO2C
EtO2C
EtO2C
EtO2C
EtO2C
I
n-Bu
+
+
2
n-Bu
n-Bu
5
6b
6a
Toluene
Dioxane
1
1
64
67
80/20
91/9
I
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
I
3
7
8a
8b
I
I
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
I
Cl
4d
Toluene
17
60
80/20
Cl
10a
+
Cl
10b
9
PhO2S
PhO2S
PhO2S
PhO2S
PhO2S
PhO2S
I
+
5
Toluene
1
ni
/
11
12b
12a
Toluene
Dioxane
1
1
48
56
80/20
80/20
I
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
+
Ph
I
Ph
6
Ph
13
14b
14a
I
TsN
15
+
TsN
16a
I
TsN
7d
Toluene
17
60
80/20
16b
a
Isolated yield.
Determined by 1H NMR spectroscopy.
Presence of the non-iodinated vinyl derivative (<10%).
Reaction at 40 ꢁC. ni: not isolated.
b
c
d

436
M. Ez-Zoubir et al. / Journal of Organometallic Chemistry 696 (2011) 433e441
additional ligand slowed the rate of the reaction, therefore the
reaction was extended to 19 h. The use of triphenylphosphine,
electron-rich or electron-poor monophosphanes and a bidentate
ligand such as diphenylphosphanoferrocene (dppf) did not lead to
significant changes for the 2a/2b ratio. We next proceeded to the
optimization of solvent (Table 2). Several polar/apolar protic/
aprotic solvents were tested including dichloromethane, dichlo-
roethane, ether, tetrahydrofuran, MeOH and dioxane (Table 2,
entries 1e6). Similar results were obtained in chlorinated solvents
compared to toluene (Table 2, entries 1e2). The use of ether at
40 ꢁC led to a lower conversion (Table 2, entry 3) albeit in excellent
selectivity. When the reaction was conducted in methanol or
tetrahydrofuran, a complete conversion was observed but several
products resulting from the degradation of 1 or 2 were present
and the isolated yields were therefore modest (Table 2, entries
4e5). The best result was obtained in dioxane, where 2a/2b were
isolated in 77% yield and a 93/7 ratio.
Fig. 1.
We therefore chose to evaluate the efficiency of the system [Ir
(cod)Cl]2 dimer in the presence of 1.1 eq.of HI in toluene and
dioxane at 80 ꢁC.
Considering the high reactivity of enynes towards the reaction
conditions, leading to several by-products, we further investigated
the hydroiodation reaction of 13 under reduced temperature
conditions (Scheme 1). Whereas the iodo derivatives 14a and 14b
were obtained at 80 ꢁC in toluene, the reaction cleanly led to the
formation of a new compound (ꢂ)-17 at 40 ꢁC. The structure of this
derivative was clearly established by proton and carbon NMR
spectroscopies and by X-Ray analysis (Fig. 1). The selective forma-
tion of (ꢂ)-17 was achieved by adding triphenylphosphane (16 mol
%) and carrying the reaction out at room temperature over 72 h, the
iodo derivative being isolated in 76% yield. In complete analogy to
previous work utilizing gold and platinum complexes in the pres-
ence of alcohols, amines or electron-rich arenes as nucleophile
[22,23], the formation of (ꢂ)-17 as the major isomer (d.r. > 90/10)
could be explained via a cycloisomerization reaction, which would
imply Iꢀ that can act as an external nucleophile. The observed
diastereoselectivity is in complete agreement with previous work
in the presence of other nucleophiles [23].
2.2. Scope and limitations
Various alkynes were explored under the optimized reaction
conditions using either toluene or dioxane as solvent. The results
are compiled in Table 3. In all cases, the reaction led to a mixture
of Markovnikov and anti-Markovnikov adducts, where the Mar-
kovnikov iodide was obtained as the major product. The dialkyl
2-(prop-2-ynyl)propanedioate derivatives could be substituted by
a phenyl, a n-butyl, a methyl or a chloride (Table 3, entries 1e4).
The mixture of iodo derivatives 4a/4b, 6a/6b, 8a/8b and 10a/10b
were isolated in 60e69% yields and in a 80/20 ratio, when the
reaction was conducted in toluene. When dioxane was used as
the solvent, a better isomer ratio was generally obtained but
depending on the substrate, the presence of the non-iodinated
alkenyl adduct was observed (Table 3, entries 1 and 2) [21]. It is
noteworthy that in the case of chloro derivative 9, the reaction
temperature was lowered to 40 ꢁC to avoid the degradation of the
product. The reaction of sulfone-substituted propargylic
compound 11 in toluene allowed the formation of iodoadducts,
which could not be isolated because of the presence of starting
material and several by-products (Table 3, entry 5). We further
pursued our study with enynes, which are important building
blocks for cycloisomerization reactions [22]. The hydroiodination
of enyne 13, bearing a cinnamyl side chain afforded the mixture
of 14a/14b in 48% isolated yield and in a 80/20 ratio (Table 3,
entry 6). The use of dioxane slightly improved the isolated yield
but did not change the a/b ratio. The N-tosyl-substituted enyne
15 was more robust at 40 ꢁC under the reaction conditions and
was transformed to the corresponding iodo derivatives 16a/16b in
60% isolated yield (Table 3, entry 7).
2.3. Mechanistic considerations
The formation of vinyliodides via a metal-catalyzed hydro-
iodination of alkynes may be explained by giving consideration to
two potential mechanisms (Scheme 2) [24]. The equilibrium
between the [Ir(cod)Cl]2 dimer and the monomer A would be fol-
lowed by the oxidative addition of HI and complexation of the
alkyne substrate leading to complex B. The presence of two isomers
may be viewed through the regiochemical outcome of the hydro-
metallation step. A regioselective hydroiridation is observed and
may be explained by the assistance of the polar functionalities such
as the ester groups or the alkenyl side chain leading to B’ type
MeO2C
14a
[Ir(cod)Cl]2 (4 mol%)
I
MeO2C
MeO2C
MeO2C
MeO2C
HI (1.1 eq.)
Ph
I
MeO2C
Ph
+
+
Ph
toluene
H
MeO2C
MeO2C
I
14b
13
( )-17
Ph
14a 14b
T = 40°C, 17 h
21
64
79 (
36 (
0
/
= 80/20)
= 80/20)
14a 14b
T = RT, 17 h
/
T = RT, 72 h, 16 mol% PPh3
100 (76% yield)
Scheme 1.

M. Ez-Zoubir et al. / Journal of Organometallic Chemistry 696 (2011) 433e441
437
MeO2C
1
Cl
CO2Me
+
Ir
[Ir(cod)Cl]2
HI
A
major
R
+
2a
I
I
2b
R
I
Ir
I
Ir
I
Ir
Cl
OMe
Cl
H
Cl
H
L
H
CO2Me
CO2Me
O
CO2Me
D
B
+
CO2Me
B'
I
L
MeO2C
Cl
O
H
Ir
OMe
favored
C
CO2Me
[Ir]
-[Ir]
I
H+
HI
[Ir]
2a
+
MeO2C
MeO2C
H+
I
1
[Ir]-
CO2Me
G
+
2b
MeO2C
CO2Me
CO2Me
F
[Ir]
E
Scheme 2.
complex. The major isomer C would then evolve to the iodo-
compound 2a via a reductive elimination. The formation of 2b
would result from the same process from complex D.
The second possible mechanism would rely on an initial
complexation of the iridium catalyst to the alkyne function leading
to the formation of intermediate E. The anti addition of Iꢀ would
afford two possible complexes F [25] and G, the latter being the
minor one. A protodemetallation step would complete the catalytic
cycle and afford 2a/2b.
pathway (Scheme 2), the existence of intermediate G being mostly
improbable. The reaction of alkyne 1 in the presence of I2 afforded
a unique diiodide derivative 18, whose structure was determined
by NOESY NMR experiment. In this case, the second mechanism
may be involved.
2.4. Palladium-catalyzed cross-coupling reactions
In order to obtain some mechanistic insight, we envisaged two
distinct experiments, one in the presence of DI and one based on
the use of I2 instead of HI (Scheme 3). When diester 7 was subjected
to the optimized conditions in the presence of DI, the formation of
8a-d1 and 8b-d1 was observed as previously. The observed deute-
rium labeling shows that both mechanisms may be advocated
(intermediates C and F) as a 1/1 mixture was obtained in the case of
8a. It is interesting to note that 8b was obtained as a unique labeled
isomer 8b-d1, which may reflect the fact that its formation (and
therefore the formation of 8b) follows the first mechanistic
The vinyliodides 2 (2a/2b ¼ 84/16) were then engaged in
palladium-catalyzed cross-coupling reactions and we turned our
attention to Sonogashira and SuzukieMiyaura reactions under mild
organoaqueous conditions (Scheme 4) [26]. The use of a catalytic
system consisting of 5 mol% Pd(OAc)2 and 15 mol% of the water-
soluble ligand tppts [27] led to the desired enynes 19, 20, and 21 in
moderate to good isolated yields. As expected, the enynes were
obtained as mixture of isomers, one may notice the lower reactivity
of 2b compared to 2a. The SuzukieMiyaura coupling was con-
ducted in the same conditions at 40 ꢁC in the presence of phenyl
D
[Ir(cod)Cl]2 (4 mol%)
I
DI (1.1 eq.)
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
MeO2C
I
D
toluene, 80 °C, 1h
60 %
+
7
8a-d1
8b-d1
E / Z = 1 / 1
E / Z = 1 / 0
I
[Ir(cod)Cl]2 (4 mol%)
I2 (1.1 eq.)
MeO2C
MeO2C
MeO2C
MeO2C
I
dioxane, 80 °C, 1h
56 %
1
18
Scheme 3.

438
M. Ez-Zoubir et al. / Journal of Organometallic Chemistry 696 (2011) 433e441
Pd(OAc)2 (5 mol%)
tppts (15 mol%)
R
MeO2C
MeO2C
2a 2b
,
+
MeO2C
MeO2C
i-Pr2NH, CH3CN/H2O
(3/1), 40°C
19-21a
19-21b
R
R
R = H, 81 % yield
R = MeO, 59% yield
R = NMe2, 42% yield
19a/19b = 95/5
20a/20b = 94/6
21a/21b = 94/6
Pd(OAc)2 (5 mol%)
tppts (15 mol%)
MeO2C
MeO2C
2a 2b
,
+
MeO2C
MeO2C
i-Pr2NH, CH3CN/H2O
(3/1), 40°C
OH
B
OH
22a
22b
60 % yield
22a 22b
/
= 93/7
Scheme 4.
boronic acid and afforded the desired alkenes 22a and 22b in 60%
isolated yield.
4.1. 1-Typical procedure for iridium-catalyzed hydroiodination
reactions
Under Argon atmosphere, a solution of substrate in anhydrous
toluene or dioxane was added to a solution of [Ir(cod)Cl]2 (4 mol%,
M ¼ 671.7) in distilled degassed toluene or dioxane. Then, an
aqueous solution of degassed HI (55e58%, ACS grade, 1.1 eq.) was
added to the mixture. The reaction was monitored by TLC and upon
completion, the mixture was filtered through a short pad of silica gel
(EtOAc) and the solvents were evaporated under reduced pressure.
The crude product was purified by silica gel flash chromatography.
3. Conclusion
The use of [Ir(cod)Cl]2 dimer associated with HI was found to be
efficient for the preparation of alkenyliodides via a hydroiodination
reaction. The reaction conditions were optimized and presented
a specific selectivity towards several functionalized alkynes bearing
esters, sulfones or alkenyl groups. In all cases, the reaction led to the
formation of a mixture of vinyliodides in good yields, where the
major adduct was the Markovnikov product. Two mechanisms
were proposed, one relying on a substrate controlled hydro-
4.2. 2-Typical procedure for palladium-catalyzed coupling reactions
The catalyst was first preformed in water by mixing 5 mol% of
palladium acetate and 15 mol% of tppts at 80 ꢁC during 30 min. To
the red colored catalyst were added at room temperature the
iodinated compound (1 eq.) in acetonitrile and then the boronic
acid (1.2 eq.) or the acetylenic compound (1.5 eq.) and finally dii-
sopropylamine (1.4 eq.). The reaction mixture was stirred at 40 ꢁC
until completion of the reaction, filtered on a short pad of silica gel
(EtOAc) and evaporated under reduced pressure. The crude product
was purified by silica gel flash chromatography.
iridation step and the other one based on p-complexation and anti
addition of the nucleophile. Further studies are directed towards
the potential generality of the iridium-catalyzed reaction for simple
alkylalkynes and aromatic ones.
4. Experimental section
[Ir(cod)Cl]2 dimer was commercially available from Cortecnet
and Acros and used without further purification. All catalytic
manipulations involving air-sensitive reagents were carried out
under argon and Schlenk techniques for catalytic tests. Toluene
and dioxane were degassed by sparging with argon and/or expo-
sure to vacuum. Column chromatography was performed with
0.040e0.063 mm Art. 11567 silica gel (E. Merck) or Florisil gel
100e200 mesh (Avocado). 1H and 13C NMR were recorded on
a Bruker AV 300 instrument. All signals were expressed as ppm
downfield from Me4Si for 1H and 13C NMR used as an internal
4.3. Dimethyl 2-(2-iodoallyl)malonate 2
Starting from 100 mg of alkyne 1 and following the typical
procedure 1 using 16.28 mg (4 mol%) of [Ir(cod)Cl]2, 86.2 ml of HI in
3 ml of toluene at 80 ꢁC in 1 h, compound 2a/b was obtained as
a pale yellow oil (127 mg, 72%). 1H NMR of the major isomer
(300 MHz, CDCl3) 2.98 (dd, J ¼ 0.7, 7.5 Hz, 2H), 3.75 (s, 6H), 3.77 (t,
J ¼ 7.5 Hz, 1H), 5.76 (d, J ¼ 1.7 Hz, 1H), 6.11e6.13 (m, 1H). 13C NMR
(75 MHz, CDCl3) 44.2, 51.3, 52.7, 105.4, 128.9, 168.4. ESI/MS (NH3):
320.7 [M þ Na]þ.
standard (d). Coupling constants (J) are reported in Hz and refer to
apparent peak multiplicities. Mass spectrometry analyses were
performed on a Varian MAT311 instrument at the Ecole Nationale
Supérieure de Chimie de Paris.
4.4. Diethyl 2-(2-iodoallyl)-2-phenylmalonate 4
Alkynes 3, 5, 7 and 9, enynes 13 and 15 were prepared
according to published procedures [23,28]. The spectral char-
acterizations of iodides 2b [29], 8a [30] and compounds 19b
[31] and 22a,b [32] are identical to those published in the
literature.
Starting from 102 mg of alkyne 3 and following the typical
procedure 1 using 10 mg (4 mol%) of [Ir(cod)Cl]2, 58 ml of HI in 2 ml of
toluene at 80 ꢁC in 17 h, compound 4a/b was obtained as a pale
yellow oil (90 mg, 60%). 1H NMR of the major isomer (300 MHz,

M. Ez-Zoubir et al. / Journal of Organometallic Chemistry 696 (2011) 433e441
439
CDCl3) 1.25 (t, J ¼ 7.1 Hz, 6H), 3.57 (d, J ¼ 0.7 Hz, 2H), 4.17e4.28 (m,
4.10. Dimethyl 3-(iodo(phenyl)methyl)-4-methylenecyclopentane-
1,1-dicarboxylate 17
4H), 5.68e5.69 (m,1H), 5.74 (d, J ¼ 2.2 Hz,1H), 7.27e7.55 (m, 5H).13C
NMR (75 MHz, CDCl3) 13.8, 50.1, 61.9,101.5,127.7,127.9,128.3,128.5,
130.3,135.0,169.2. DCI/MS (NH3): 403.0 [M þ H]þ, 420.0 [M þ NH4]þ.
In a mixture of [Ir(cod)Cl]2 (4.8 mg, 4 mol%) and PPh3 (7.6 mg,
16 mol%) was added 0.5 ml of anhydrous toluene. The homoge-
neous mixture was stirred at room temperature during 1 h. Then,
a solution of enyne 13 (50 mg) in 0.5 ml of toluene was added,
4.5. Diethyl 2-n-butyl-2-(2-iodoallyl)malonate 6
following by the addition of 26 ml of aqueous solution of degassed
Starting from 100 mg of alkyne 5 and following the typical
HI (55e58%, ACS grade, 1.1 eq.). The reaction mixture was stirred
72 h at room temperature and the crude product was filtered
through a short pad of silica gel (EtOAc). Solvents were removed
under reduced pressure and the crude product was purified by
silica gel flash chromatography (cyclohexane/EtOAc, 90/10),
compound 17 was obtained as a yellow solid (55 mg, 76%). 1H NMR
(300 MHz, CDCl3) 2.26e2.35 (m,1H), 2.83e3.10 (m, 4H), 3.72(s, 3H),
3.77 (s, 3H), 4.38e4.40 (m, 1H), 4.94 (m, 1H), 5.17 (d, J ¼ 8.2 Hz, 1H),
7.22e7.41 (m, 5H). 13C NMR (75 MHz, CDCl3) 40.7, 41.9, 42.8, 49.8,
52.9, 57.9, 110.7, 128.0, 128.3, 128.5, 143.2, 147.3, 171.5, 171.7. DCI/MS
(CH4): 415.0 [M þ H]þ.
procedure 1 using 10.9 mg (4 mol%) of [Ir(cod)Cl]2, 57 ml of HI in
2.1 ml of toluene at 80 ꢁC in 17 h, compound 6a/b was obtained as
a pale yellow oil (100 mg, 66%). 1H NMR of the major isomer
(300 MHz, CDCl3) 0.88 (t, J ¼ 7.1 Hz, 3H), 1.07e1.14 (m, 2H), 1.19 (t,
J ¼ 7.0 Hz, 6H), 1.31 (m, 2H), 1.95e2.03 (m, 2H), 3.13 (d, J ¼ 0.9 Hz,
2H), 4.13e4.27 (m, 4H), 5.90 (d, J ¼ 1.5 Hz, 1H), 6.11 (d, J ¼ 1.1 Hz,
1H). 13C NMR (75 MHz, CDCl3) 13.8, 14.1, 22.7, 26.0, 30.9, 32.2, 45.7,
57.4, 61.3, 101.5, 130.7, 170.6. DCI/MS (NH3): 383.1 [M þ H]þ, 400.1
[M þ NH4]þ.
4.6. Dimethyl 2-(2-iodoallyl)-2-methylmalonate 8
Starting from 100 mg of alkyne 7 and following the typical
4.11. (E)-Dimethyl 2-(2,3-diiodoallyl)malonate 18
procedure 1 using 15 mg (4 mol%) of [Ir(cod)Cl]2, 80 ml of HI in
2.75 ml of dioxane at 80 ꢁC in 1 h, compound 8a/b was obtained as
Under inert atmosphere (Ar), a solution of 1 (50 mg) in
anhydrous dioxane (1.5 ml) was added to a mixture of [Ir(cod)
Cl]2 (8.14 mg, 4 mol%, M ¼ 671.7) and I2 (82 mg, 1.1 eq.,
M ¼ 253.81). After 1 h at 80 ꢁC, the mixture was filtered through
a short pad of silica gel (EtOAc) and the solvents were evapo-
rated under reduced pressure. The crude product was purified
by silica gel flash chromatography and compound 18 was
obtained as colorless oil (69 mg, 56%). 1H NMR (300 MHz, CDCl3)
3.10 (dd, J ¼ 0.6, 7.5 Hz, 2H), 3.77 (s, 6H), 3.80 (t, J ¼ 7.5 Hz, 1H),
7.04 (d, J ¼ 0.6 Hz, 1H) 13C NMR (75 MHz, CDCl3) 43.3, 50.8, 52.9,
a pale yellow oil (112 mg, 67%).
4.7. Dimethyl 2-chloro-2-(2-iodoallyl)malonate 10
Starting from 100 mg of alkyne 9 and following the typical
procedure 1 using 13.55 mg (4 mol%) of [Ir(cod)Cl]2, 71 ml of HI in
2.6 ml of toluene at 40 ꢁC in 17 h, compound 10a/b was obtained as
a pale yellow oil (100 mg, 60%). 1H NMR of the major isomer
(300 MHz, CDCl3) 3.44 (d, J ¼ 1.1 Hz, 2H), 3.84 (s, 6H), 6.01 (d,
J ¼ 1.8 Hz, 1H), 6.28 (d, J ¼ 1.8 Hz, 1H) 13C NMR (75 MHz, CDCl3)
50.8, 54.1, 68.4, 96.9, 132.9, 137.8, 166.1 DCI/MS (NH3): 332.9
[M þ H]þ, 349.5 [M þ NH4]þ.
82.9, 97.9, 168.0. DCI/MS (NH3): 424.9 [M
þ
H]þ, 441.9
[M þ NH4]þ.
4.12. Dimethyl 2-(2-methylene-4-phenylbut-3-yn-1-yl)malonate 19
4.8. Dimethyl 2-cinnamyl-2-(2-iodoallyl)malonate 14
Starting from 50 mg of compound 2a/b and following the typical
procedure 2 using 1.9 mg (5 mol%) of Pd(OAc)2,14.3 mg (15 mol%) of
tppts, 28 ml (1.5 eq.) of phenylacetylene and 32.5 ml (1.4 eq.) of the
Starting from 100 mg of enyne 13 and following the typical
procedure 1 using 9.70 mg (4 mol%) of [Ir(cod)Cl]2, 52 ml of HI in
1.9 ml of toluene at 80 ꢁC in 1 h, compound 14a/b was obtained as
a pale brown oil (72 mg, 48%). 1H NMR of the major isomer
(300 MHz, CDCl3) 2.91 (dd, J ¼ 1.3, 7.5 Hz, 2H), 3.21 (d, J ¼ 0.9 Hz,
2H), 3.7 (s, 6H), 5.97 (d, J ¼ 1.5 Hz, 1H), 6.0 (dt, J ¼ 7.5, 15.8 Hz, 1H),
6.20 (d, J ¼ 1.5 Hz, 1H), 6.45 (d, J ¼ 15.8 Hz, 1H), 7.21e7.36 (m, 5H)
13C NMR (75 MHz, CDCl3) 35.6, 46.5, 52.7, 57.8, 100.9, 123.5, 126.2,
127.5, 128.5, 131.4, 134.4, 136.9, 170.4. DCI-MS (NH3) 415 [M þ H]þ
432 [M þ NH4]þ.
diisopropylamine in acetonitrile/water (1.2 ml/0.4 ml) at 40 ꢁC in
1.5 h, compound 19a/b was obtained as a brown oil (37 mg, 81%). 1H
NMR of the major isomer (300 MHz, CDCl3) 2.87 (d, J ¼ 7.8 Hz, 2H),
3.75 (s, 6H), 3.81 (t, J ¼ 7.8 Hz, 1H), 5.40 (d, J ¼ 1.5 Hz, 1H), 5.48 (m,
1H), 7.30e7.46 (m, 5H) 13C NMR (75 MHz, CDCl3) 36.2, 50.7, 52.6,
88.0, 90.4, 122.7, 123.8, 127.3, 128.4, 128.5, 131.5, 169.1 DCI/MS
(NH3): 273.1 [M þ H]þ, 290.1 [M þ NH4]þ.
4.9. N-(Cyclohex-2-en-1-yl)-N-(2-iodoallyl)-4-
4.13. Dimethyl 2-(4-(4-methoxyphenyl)-2-methylenebut-3-yn-1-
methylbenzenesulfonamide 16
yl)malonate 20
Starting from 100 mg of enyne 15 and following the typical
Starting from 50 mg of compound 2a/b and following the typical
procedure 1 using 9.6 mg (4 mol%) of [Ir(cod)Cl]2, 51
m
l of HI in
procedure 2 using 1.88 mg (5 mol%) of Pd(OAc)2, 14.3 mg (15 mol%)
1.9 ml of toluene at 40 ꢁC in 17 h, compound 16a/b was obtained
as a yellow solid (90 mg, 61%). 1H NMR of the major isomer
(300 MHz, CDCl3) 1.38e1.93 (m, 6H), 2.43 (s, 3H), 3.67 (dt, J ¼ 1.5,
18.2 Hz, 1H), 4.07 (dt, J ¼ 1.5, 18.2 Hz, 1H), 4.48e4.56 (m, 1H),
4.83e4.88 (m, 1H), 5.76e5.82 (m, 1H), 5.90e5.92 (m, 1H),
6.56e6.58 (m, 1H), 7.28 (d, J ¼ 8.1 Hz, 2H), 7.70 (d, J ¼ 8.1, 2H). 13C
NMR (75 MHz, CDCl3) 21.4, 21.6, 24.4, 29.3, 55.4, 55.6, 107.6,
125.8, 126.1, 127.1, 129.8, 133.6, 137.5, 143.5 DCI/MS (NH3): 418.0
[M þ H]þ, 435.0 [M þ NH4]þ.
of tppts, 33 ml (1.5 eq.) of p-methoxy-phenylacetylene and 32.5 ml
(1.4 eq.) of the diisopropylamine in acetonitrile/water (1.2 ml/
0.4 ml) at 40 ꢁC in 2 h, compound 20a/b was obtained as a orange oil
(30 mg, 59%). 1H NMR of the major isomer (300 MHz, CDCl3) 2.87
(dd, J ¼ 0.4, 7.6 Hz, 2H), 3.73 (s, 6H), 3.80 (s, 3H), 3.83 (t, J ¼ 7.6 Hz,
1H), 5.35e5.36 (m, 1H), 5.43e5.44 (m, 1H), 6.85 (d, J ¼ 8.9 Hz, 2H),
7.39 (d, J ¼ 8.9 Hz, 2H), 13C NMR (75 MHz, CDCl3) 36.3, 50.7, 52.6,
55.3, 86.8, 90.5, 113.9, 114.9, 122.9, 127.5, 132.9, 133.1, 159.7, 169.1.
DCI/MS (NH3): 303.1 [M þ H]þ, 320.1 [M þ NH4]þ.

440
M. Ez-Zoubir et al. / Journal of Organometallic Chemistry 696 (2011) 433e441
(c) For anapplicationofthis methodology intotal synthesis, seeD.W.C.MacMillan,
L.E. Overman, L.D. Pennington, J. Am. Chem. Soc. 123 (2001) 9033.
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(b) K. Takami, S. Mikami, S.H. Yorimitsu, H. Shinokubo, K. Oshima, J. Org.
Chem. 68 (2003) 6627;
4.14. Dimethyl 2-(4-(4-(dimethylamino)phenyl)-2-methylenebut-
3-yn-1-yl)malonate 21
Starting from 50 mg of compound 2a/b and following the typical
procedure 2 using 1.88 mg (5 mol%) of Pd(OAc)2, 14.3 mg (15 mol%)
of tppts, 38 mg (1.5 eq.) of p-dimethylamine-phenylacetylene and
(c) G. Dumartin, J. Kharboutli, B. Delmond, Y. Frangin, M. Pereyre, Eur. J. Org.
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ml (1.4 eq.) of the diisopropylamine in acetonitrile/water
(1.2 ml/0.4 ml) at 40 ꢁC in 17 h, compound 21a/b was obtained as
a brown oil (22 mg, 42%). 1H NMR of the major isomer (300 MHz,
CDCl3) 2.84 (d, J ¼ 7.6 Hz, 2H), 2.97 (s, 6H), 3.74 (s, 6H), 3.82 (t,
J ¼ 7.6 Hz, 1H), 5.30 (d, J ¼ 1.5 Hz, 1H), 5.43 (d, J ¼ 1.5 Hz, 1H), 6.85
(d, J ¼ 8.9 Hz, 2H), 7.39 (d, J ¼ 8.9 Hz, 2H) 13C NMR (75 MHz, CDCl3)
36.5, 40.1, 50.8, 52.6, 86.1, 91.8, 109.5, 111.7, 121.9, 127.9, 132.6, 150.1,
169.3. DCI/MS (NH3): 316.1 [M þ H]þ, 333.2 [M þ NH4]þ.
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4.15. Dimethyl 2-(2-phenylallyl)malonate 22
Starting from 100 mgof compound 2a/b and following the typical
procedure 2 using 3.8 mg (5 mol%) of Pd(OAc)2, 28.60 mg (15 mol%)
of tppts, 50.1 mg (1.2 eq.) of phenyl boronic acid and 65 ml (1.4 eq.) of
the diisopropylamine in acetonitrile/water (2.4 ml/0.8 ml) at 40 ꢁC in
17 h, compound 22a/b was obtained as a colorless oil (50 mg, 60%).
Acknowledgments
J. Barluenga, M.A. Rodriguez, P.J. Campos, J. Chem. Soc. Chem. Commun.
(1990) 2807;
(c) For a recent metal-catalyzed hydroiodation of alkenes, see B. Gaspar,
E.M. Carreira, Angew. Chem. Int. Ed. 47 (2008) 5758.
This work was supported by the Centre National de la
Recherche Scientifique (CNRS) and the Ministère de l’Education et
de la Recherche for financial support. M. E.-Z. is grateful to the
Centre National de la Recherche Scientifique and GlaxoSmithkline
for a grant (2007e2010). The authors thank Dr. M.-N. Rager
(Chimie ParisTech) for NOESY experiments and L.-M. Chamoreau
(Laboratoire de Chimie Inorganique et Matériaux Moléculaires,
Paris) for X-Ray structure analysis. Johnson-Matthey is acknowl-
edged for a generous loan of PdCl2 and PtCl2. The authors also
thank Dr. T. Schlama (Rhodia) for generous gift of tppts ligand.
[17] S.A. Mitchenko, V.V. Zamashchikov, A.A. Shubin, Kinet. Catal. 34 (1993) 421.
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V. Michelet, Chem. Commun. 46 (2010) 6332.
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Appendix. Supporting information
Supporting information associated with this article can be found,
in the online version, at doi:10.1016/j.jorganchem.2010.10.052.
(b) M. Méndez, M.P. Muñoz, A.M. Echavarren, J. Am. Chem. Soc. 122 (2000)
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M. Méndez, M.-N. Rager, J.-P. Genêt, A.M. Echavarren, Eur. J. Org. Chem. (2003)
706;
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