Electron-poor chiral diphosphine ligands: High performance for rh-catalyzed asymmetric 1,4-addition of arylboronic acids at room temperature

Article abstract of DOI:10.1021/ol900719z

Electron-poor chiral diphosphine ligands, MeO-F28-BIPHEP (1a) and MeO-F12-BIPHEP (1b), were synthesized for controlling a transition-metal catalyst electronically. The 1b-ligated Rh catalyst showed excellent catalytic activity with high % ee for asymmetri

Full text of DOI:10.1021/ol900719z

ORGANIC
LETTERS
2
009
Vol. 11, No. 11
325-2328
Electron-Poor Chiral Diphosphine
Ligands: High Performance for
Rh-Catalyzed Asymmetric 1,4-Addition
of Arylboronic Acids at Room
Temperature
2
Toshinobu Korenaga,* Kazutaka Osaki, Ryota Maenishi, and Takashi Sakai*
DiVision of Chemistry and Biochemistry, Graduate School of Natural Science and
Technology, Okayama UniVersity, 3-1-1 Tsushima-naka, Okayama 700-8530, Japan
korenaga@cc.okayama-u.ac.jp
Received April 6, 2009
ABSTRACT
Electron-poor chiral diphosphine ligands, MeO-F28-BIPHEP (1a) and MeO-F12-BIPHEP (1b), were synthesized for controlling a transition-metal
catalyst electronically. The 1b-ligated Rh catalyst showed excellent catalytic activity with high % ee for asymmetric 1,4-addition of arylboronic
acids to r,ꢀ-unsaturated carbonyls at 20 °C. The strong π-acceptor ability of 1b induces transmetalation of arylboronic acid to catalyst
2
precursor [RhCl(1b)] directly in the first step of the catalytic cycle.
Phosphine ligands have played a significant role in both steric
and electronic adjustment of transition-metal-catalyzed reac-
tions. Although a large majority of phosphine ligands are
poor diphosphine ligands are well-suited to take full advan-
tage of the π-acceptor character for controlling the catalyst
electronically. Specifically, a biaryl diphosphine (BINAP-
1
4
more electron-rich than triphenylphosphine, there are quite
type) ligand, which has a biaryl backbone and two arylphos-
a few examples of applications of electron-poor phosphine
ligands, in particular, fluorinated aryl phosphines. However,
phorus substituents, has the highest potential due to its
flexibility for facile complexation with metals and its
2
only a few examples of those chiral ligands having prominent
catalytic effects have been reported in asymmetric reactions,
3
(3) (a) Jana, C. K.; Studera, A. Angew. Chem., Int. Ed. 2007, 46, 6542.
(
b) Tani, K.; Behenna, D. C.; McFadden, R. M.; Stoltz, B. M. Org. Lett.
and most of them concern P,N-ligands bearing both electron-
2007, 9, 2529. (c) Moran, W. J.; Morken, J. P. Org. Lett. 2006, 8, 2413.
d) Legault, C. Y.; Charette, A. B. J. Am. Chem. Soc. 2005, 127, 8966. (e)
3b-e
(
poor phosphorus and donative nitrogen atoms.
Electron-
Garcia-Yebra, C.; Janssen, J. P.; Rominger, F.; Helmchen, G. Organome-
tallics 2004, 23, 5459. (f) Hayashi, T.; Hirate, S.; Kitayama, K.; Tsuji, H.;
Torii, A.; Uozumi, Y. J. Org. Chem. 2001, 66, 1441.
(
1) (a) Surry, D. S.; Buchwald, S. L. Angew. Chem., Int. Ed. 2008, 47,
338. (b) Valentine, D. H., Jr.; Hillhouse, J. H. Synthesis 2003, 2437.
2) Pollock, C. L.; Saunders, G. C.; Smyth, E. C. M. S.; Sorokin, V. I.
J. Fluorine Chem. 2008, 129, 142.
6
(4) (a) Berthod, M; Mignani, G.; Woodward, G.; Lemaire, M. Chem.
ReV. 2005, 105, 1801. (b) Shimizu, H.; Nagasaki, I.; Saito, T. Tetrahedron
2005, 61, 5405. (c) Noyori, R.; Takaya, H. Acc. Chem. Res. 1990, 23, 345.
(
1
0.1021/ol900719z CCC: $40.75  2009 American Chemical Society
Published on Web 05/11/2009

4
c
5b
paramount steric influence for high asymmetric induction.
are lower than those of electron-poor Difluorphos. The
Although many BINAP-type ligands have been reported, it
is surprising that few have been reported for the ligand
results promise the effectiveness of the ligands 1a and 1b
as strong π-acceptor ligand for transition metal catalysis.
Novel ligands 1a and 1b were synthesized according to
the preparation methods of MeO-BIPHEP analogues from
(R)- or (S)-2 (Scheme 1). The compound 2 was treated with
5,6
bearing fluorine atoms. In addition, those ligands have only
one or two fluoro-functional groups on each monoaromatic
ring, and accordingly they should be endowed with an
insufficient π-acceptor ability. In this Letter, we report the
development of novel electron-poor BINAP-type ligands 1,
7
7
which are MeO-BIPHEP analogues bearing three or more
Scheme 1. Synthesis of Electron-Poor Diphosphine Ligands 1
fluoro-functional groups on each phosphorus phenyl ring.
These groups would incorporate not only strong π-acceptor
ability but also steric bulkiness into the chiral diphosphine.
The performance of ligands 1 was demonstrated by using
8
Rh-catalyzed asymmetric 1,4-addition.
We designed MeO-F28-BIPHEP (1a) and MeO-F12-BI-
PHEP (1b) as shown in Figure 1. These potentials were
7 7 6 3 2
an excess of C F Li or C F H MgBr in THF at -80 °C to
give the corresponding enantiomer of 1a or 1b in a moderate
yield, respectively.
The electronic properties of 1 were estimated by com-
parison with the carbonyl stretching frequencies (VCO) of the
5
b
corresponding [RhCl(diphosphine)(CO)] complexes 3,
which were prepared from [RhCl(CO)] . The VCO value of
b is higher than those of known diphosphines including
2
3
electron-poor ones, indicating that 1b has sufficient π-acidic
character as compared with the known diphosphines (Table
1
). Unfortunately, 3a could not be prepared by the reaction
Table 1. Electronic Properties of 1a and 1b
diphosphine
(L*)
vCO of [RhCl(L*)(CO)] reduction potential of
-
1
d
Figure 1
complex.
.
Ability of electron-poor diphosphine ligands 1 on metal
(cm
)
[PtCl (L*)] (V)
2
1
a
- [3a]
-1.49 [5a]
-1.77 [5b]
-1.94
a
1
b
2036 [3b]
b
MeO-BIPHEP
BINAP
p-F-BINAP
difluorophos
2014
b
predicted by DFT calculations of Pt complexes at the
B3LYP/6-31G* (LANL2DZ for Pt) level (Figure 1). The
energies of the HOMO and LUMO of both Pt-1a and Pt-1b
2017
9
c
2018
b
2023
a
b
c
d
In CHCl
3
.
From ref 5b. From ref 5h. See Supporting Information.
(
5) (a) Kim, D. E.; Choi, C.; Kim, I. S.; Jeulin, S.; Ratovelomanana-
Vidal, V.; Genet, J.-P.; Jeong, N. Synthesis 2006, 4053. (b) Jeulin, S.; Duprat
de Paule, S.; Ratovelomanana-Vidal, V.; Genet, J.-P.; Champion, N.; Dellis,
P. Angew. Chem., Int. Ed. 2004, 43, 320. (c) Driessen-Hoelscher, B.; Kralik,
J.; Agel, F.; Steffens, C.; Hu, C. AdV. Synth. Catal. 2004, 346, 979. (d)
Jeong, N.; Kim, D. H.; Choi, J. H. Chem. Commun. 2004, 1134. (e) Scalone,
M.; Waldmeier, P. Org. Process Res. DeV. 2003, 7, 418. (f) Koh, J. H.;
Larsen, A. O.; Gagne, M. R. Org. Lett. 2001, 3, 1233. (g) Jendralla, H.; Li,
C. H.; Paulus, E. Tetrahedron: Asymmetry 1994, 5, 1297. (h) Mashima,
K.; Kusano, K.; Sato, N.; Matsumura, Y.; Nozaki, K.; Kumobayashi, H.;
Sayo, N.; Hori, Y.; Ishizaki, T.; Akutagawa, S.; Takaya, H. J. Org. Chem.
2 2 2
of 1a with [RhCl(CO) ] , which gave [RhCl(1a)] (4a),
suggesting that 1a has strong π-acceptor ability. To
10
(9) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Montgomery, J. A.; Jr. Vreven, T.; Kudin, K. N.;
Burant, J. C.; Millam, J. M.; Iyengar, S. S; Tomasi, J.; Barone, V.; Mennucci,
B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.;
Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.;
Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox,
J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.;
Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.;
Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.;
Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels,
A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.;
Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.;
Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz,
P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.;
Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson,
B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03,
ReVision E.01; Gaussian, Inc.: Pittsburgh, PA, 2004.
1
8
994, 59, 3064. (i) Murata, M.; Morimoto, T.; Achiwa, K. Synlett 1991,
27
.
(
6) Among them, Difluorphos (ref 5b) has been used recently. (a) Liao,
X.; Weng, Z.; Hartwig, J. F. J. Am. Chem. Soc. 2008, 130, 195. (b) Du, Y.;
Xu, L.-W.; Shimizu, Y.; Oisaki, K.; Kanai, M.; Shibasaki, M. J. Am. Chem.
Soc. 2008, 130, 16146. (c) Oisaki, K.; Zhao, D.; Kanai, M.; Shibasaki, M.
J. Am. Chem. Soc. 2007, 129, 7439. (d) Yamamoto, Y.; Yamamoto, H.
Angew. Chem., Int. Ed. 2005, 44, 7082
.
(
7) Schmid, R.; Broger, E. A.; Cereghetti, M.; Crameri, Y.; Foricher,
J.; Lalonde, M.; Muller, R. K.; Scalone, M.; Schoettel, G.; Zutter, U. Pure
Appl. Chem. 1996, 68, 131.
(8) Hayashi, T.; Takahashi, M.; Takaya, Y.; Ogasawara, M. J. Am. Chem.
Soc. 2002, 124, 5052.
2326
Org. Lett., Vol. 11, No. 11, 2009

evaluate 1a, cyclic voltammetries were examined for air-
stable [PtCl (1)] (5), which was prepared from [PtCl
PhCN) ]. The reduction potential increased with the in-
2
2
-
Table 2. Rh-Catalyzed Asymmetric 1,4-Addition
(
2
creasing number of fluorine atoms in 5 (Table 1), indicating
that the π-acceptor ability of the fluoroaromatic group on
phosphorus has a significant effect on the orbital energy of
the central metal.
The performance of the electron-poor ligands 1 was
Rh
temp time yield
ee
(%)
evaluated by the Rh-catalyzed 1,4-addition of PhB(OH)
2
to
f
entry
(R)-L*
1a
1a
1b
1b
1b
1b
1b
(%) solvent
(°C)
(h)
(%)
8
2
-cyclohexenone. It was expected that the electron-poor
a
11
12
1
2
3
4
5
6
7
8
3.0 dioxane
3.0 toluene
3.0 dioxane
3.0 dioxane
3.0 toluene
3.0 toluene
0.2 toluene
0.1 toluene
3.0 dioxane
3.0 toluene
3.0 dioxane
3.0 dioxane
3.0 toluene
c
35
20
35
20
20
20
20
20
20
20
35
20
20
d
3
3
3
5
3
3
1
1
5
3
3
5
3
10
86
98
68
99
52
98
75
39
0
97
96
>99
99
>99
>99
>99
>99
99
ligand would accelerate both transmetalation and insertion
b
8
steps in the catalytic cycle. To start with, we examined the
preparation of 4a (see above) and [RhCl(1b)] (4b), which
were used for the catalyst precursor. Complex (R,R)-4b was
readily prepared from (R)-1b using [RhCl(C . The
X-ray crystal structure of (R,R)-4b (see Supporting Informa-
tion) was compared with that of [RhCl{(R)-binap}] [(R,R)-
a
2
a
8
b
c
H ) ]
2 4 2 2
d
d
1b
2
a
e
e
1
3
9
BIPHEP
BIPHEP
BINAP
BINAP
BINAP
b
4
2
[
c]. The Rh-P lengths of the (R,R)-4b [2.195(3) and
b
10
11
12
13
a
.200(3) Å] and the bite angle (P-Rh-P) of 1b in (R,R)-4b
91.22(11)°] are similar to those of (R,R)-4c. Although the
a
a
b
94
30
0
99
97
Rh-Cl length of (R,R)-4b is similar to that of (R,R)-4c, the
angle of Rh-Cl-Rh in (R,R)-4b is larger by ca. 10°. As a
result, the Rh···Rh distance in (R,R)-4b (3.511 Å) is signifi-
cantly longer than that of (R,R)-4c (3.287 Å). The elongation
results from weakening the interaction between Rh···Rh with
less σ-donating ligand, which is unfavorable for the dz2 orbital
e
3
0% KOH. 50% KOH. Without KOH. 20% KOH. MeO-BIPHEP.
f
Isolated yield.
The catalytic activities of 1a and 1b were dramatically
improved by changing the solvent to toluene (entries 2 and
). In particular, (R)-1b increased the rate of reaction, where
the amount of Rh could be reduced to 0.2 mol % without
loss of yield under the mild conditions for 1 h (entry 7).
The turnover frequency (TOF) reaches 750 h (entry 8).
Although the TOF value did not come close to the best result
on the same reaction, it is worthy of attention that our
catalytic system achieves both high catalytic activity and
almost complete enantioselectivity by using stoichiometric
2
PhB(OH) at room temperature. In contrast, the catalysts
with (R)-BINAP or (R)-MeO-BIPHEP showed no catalytic
1
4
of Rh.
Asymmetric 1,4-addition reactions were carried out ac-
cording to the standard conditions [1.5 mol % [RhCl(C
3 mol % Rh) with diphosphine for in situ formation of 4,
.5 equiv of PhB(OH) (7a) for 2-cyclohexenone (6a) with
KOH in dioxane/H O, at 35 °C for 3 h] (Table 2). Although
R)-1a was found to be less effective, (R)-1b provided the
5
2 4 2 2
H ) ]
(
2
-
1
2
8
2
1
7
1
5
(
1
8
8
successful result comparable to that using (R)-BINAP in
both yield and % ee of (R)-8aa (entry 1 vs 3 vs 11). Under
1
9
milder conditions [1.05 equiv of PhB(OH)
b still gave 99% enantioselectivity with a yield much higher
2
at 20 °C], (R)-
1
activity in toluene (entries 10 and 13). Although conversion
1
6
than that in the case of (R)-BINAP (entry 4 vs 12). The
result is attributed to the electronic effect of the ligand,
because the reaction using (R)-MeO-BIPHEP, which bears
same backbone as 1, gave a result similar to that using (R)-
BINAP (entry 9).
(
17) Hayashi et al. reported that the reaction using 0.05 mol % of the
Rh catalyst and 1.2 equiv of 7a at 30 °C for 1 h gave 95% of product with
-
1
9
3
6% ee (TOF ) 1900 h ) and the use of (PhBO) instead of 7a gave a
-1
TOF value of 14000 h . Minnaard and Feringa et al. reported that the
reaction using 0.05 mol % of the Rh catalyst and 3 equiv of 7a at 80 °C for
-
1
2
h gave 100% of product with >98% ee (TOF ) 1000 h ). (a) Chen,
F.-X.; Kina, A.; Hayashi, T. Org. Lett. 2006, 8, 341. (b) Boiteau, J.-G.;
Minnaard, A. J.; Feringa, B. L. J. Org. Chem. 2003, 68, 9481.
(10) Atherton, M. J.; Coleman, K. S.; Fawcett, J.; Holloway, J. H.; Hope,
E. G.; Karacar, A.; Peck, L. A.; Saunders, G. C. J. Chem. Soc., Dalton
Trans. 1995, 4029.
(18) Except for the prominent results in ref 17, the TOF values of most
catalytic systems are less than 100 in Rh-catalyzed asymmetric 1,4-addion
(
(
11) Clarke, M. L.; Heydt, M. Organometallics 2005, 24, 6475.
2
of PhB(OH) to 1,2-cyclohexenone.
12) Chen, Q.; Lin, B.-L.; Fu, Y.; Liu, L.; Guo, Q.-X. Res. Chem.
(19) The same reaction as shown in Table 2 at room temperature (20-25
°C). (a) Lukin, K.; Zhang, Q.; Leanna, M. R. J. Org. Chem. 2009, 74, 929.
(b) Mariz, R.; Luan, X.; Gatti, M.; Linden, A.; Dorta, R. J. Am. Chem.
Soc. 2008, 130, 2172. (c) Okamoto, K.; Hayashi, T.; Rawal, V. H. Org.
Lett. 2008, 10, 4387. (d) Gendrineau, T.; Chuzel, O.; Eijsberg, H.; Genet,
J.-P.; Darses, S. Angew. Chem., Int. Ed. 2008, 47, 7669. (e) Feng, C.-G.;
Wang, Z.-Q.; Shao, C.; Xu, M.-H.; Lin, G.-Q. Org. Lett. 2008, 10, 4101.
(f) No e¨ l, T.; Vandyck, K.; Eycken, J. V. Tetrahedron 2007, 63, 12961. (g)
Monti, C.; Gennari, C.; Piarulli, U. Chem. Eur. J. 2007, 13, 1547. (h)
Kurihara, K.; Sugishita, N.; Oshita, K.; Piao, D.; Yamamoto, Y.; Miyaura,
N. J. Organomet. Chem. 2007, 692, 428. (i) Berthon-Gelloz, G.; Hayashi,
T. J. Org. Chem. 2006, 71, 8957. (j) Martina, S. L. X.; Minnaard, A. J.;
Hessen, B.; Feringa, B. L. Tetrahedron Lett. 2005, 46, 7159. (k) Defieber,
C.; Paquin, J.-F.; Serna, S.; Carreira, E. M. Org. Lett. 2004, 6, 3873. (l)
Hayashi, T.; Ueyama, K.; Tokunaga, N.; Yoshida, K. J. Am. Chem. Soc.
2003, 125, 11508.
Intermed. 2005, 31, 759.
13) Bunten, K. A.; Farrar, D. H.; Poe, A. J.; Lough, A. Organometallics
002, 21, 3344.
14) Aull o´ n, G.; Ujaque, G.; Lled o´ s, A.; Alvarez, S.; Alemany, P. Inorg.
Chem. 1998, 37, 804–813.
15) The low catalytic activity of the Rh-1a catalyst can perhaps be
(
2
(
(
attributed to a steric effect of the 2,6-position of the fluorine atom in the
Ar group: Clarke, M. L.; Ellis, D.; Mason, K. L.; Orpen, A. G.; Pringle,
P. G.; Wingad, R. L.; Zaher, D. A.; Baker, R. T. Dalton Trans. 2005, 7,
1
294.
(
16) The result that the electron-poor ligand is superior to BINAP is
consistent with those of Rh-catalyzed 1,4-addition to other R,ꢀ-unsaturat-
ed substrates by using Difluorophos. (a) Navarre, L.; Martinez, R.; Genet,
J.-P.; Darses, S. J. Am. Chem. Soc. 2008, 130, 6159. (b) Sibi, M. P.;
Tatamidani, H.; Patil, K. Org. Lett. 2005, 7, 2571.
Org. Lett., Vol. 11, No. 11, 2009
2327

of both (R,R)-4b and (R,R)-4c to the active species of
variety of arylboronic acids 7, and cyclic and acyclic enones
6 to give good yields and enantioselectivities (Table. 3).
8
[
2
RhOH(diphosphine)] (9) by KOH in dioxane for 1 h was
3
1
observed by P NMR (Supporting Information), these
complexes 4 were not transformed at all when toluene was
used as the solvent (Figure 2a,b for 4b). Surprisingly,
Table 3. Rh-Catalyzed Asymmetric 1,4-Addition
time yield
ee
entry
6
Ar of boronic acid (7)
(h)
(%)
(%)
1
2
3
6a 3-MeC
6a 4-MeC
6a 3-MeOC
6
H
H
4
(7b) (1.05 equiv)
(7c) (1.05 equiv)
0.5
0.5
1.0
0.5
0.5
0.5
0.5
0.5
3.0
3.0
1.0
0.5
92
92
94
85
97
89
86
96
31
96
90
99
>99
99
99
>99
>99
>99
>99
90
98
98
>99
99
6
4
6
H
4
(7d) (1.05 equiv)
a
4
5
6a 3-FC
6a 3-FC
6a 4-FC
6a 4-CF
6
6
6
3
H
H
H
4
4
4
(7e) (1.05 equiv)
(7e) (1.20 equiv)
(7f) (1.20 equiv)
Figure 2 31P NMR of Rh complexes in toluene.
.
a
6
7
8
6 4
C H (7g) (1.05 equiv)
precursor 4b itself showed the catalytic activity without KOH
6b Ph (7a) (1.05 equiv)
6c Ph (7a) (1.50 equiv)
6c Ph (7a) (1.50 equiv)
2
0
to give (R)-8aa in a moderate yield (entry 6). Therefore,
R,R)-4b undergoes transmetalation with 7a directly in
consequence of the strong π-acceptor ability of 1b (Figure
), while BINAP does not have such activity. At the end of
9
b
10
11
12
a
(
6d 4-CF
3
C
6
H
4
(7g) (1.05 equiv)
6e Ph (7a) (1.30 equiv)
3
b
4
0% of KOH. At 30 °C.
In conclusion, we have succeeded to develop novel and
highly electron-poor chiral diphosphine ligands 1. The strong
π-acceptor ability of 1b was found to greatly improve the
catalytic activity for Rh-catalyzed 1,4-addition at room
temperature. The utility of 1b is especially promising for
other asymmetric catalytic reactions that can be accelerated
by π-acceptor ligands.
Figure 3. Plausible mechanism using (R,R)-4b in toluene.
Acknowledgment. This work was supported by Mitsui
Chemicals Award in Synthetic Organic Chemistry, Japan and
a Grant-in-Aid for Young Scientists (B) from the Ministry
of Education, Culture, Sports, Science and Technology,
Japan. We thank Professor H. Tanaka, Dr. M. Kuroboshi
and Dr. T. Oshiki (Okayama University) for the CV and
X-ray diffraction analysis, respectively.
the reaction of entry 6 or 7, the resulting Rh complex was
RhOH[(R)-1b]} [(R,R)-9b], and 4b could not be observed
by P NMR (Figure 2c). The result suggested that 9b acts
{
2
3
1
as the active species after the second catalytic cycle just as
8
in the standard Rh-catalyzed 1,4-addition. In toluene, KOH
2
0
serves to accelerate the transmetalation of 7a.
Supporting Information Available: Experimental details,
NMR data, figure of CV, Ortep drawing of (R,R)-4b, and
CIF file. This material is available free of charge via the
Internet at http://pubs.acs.org.
The Rh catalyst with 1b is effective for other substrates.
The reactions using 0.5% Rh were successfully applied to a
(
2
20) The [RhCl(cod)] complex without KOH showed no catalytic
activity at low temperature. Itooka, R.; Iguchi, Y.; Miyaura, N. J. Org.
Chem. 2003, 68, 6000.
OL900719Z
2328
Org. Lett., Vol. 11, No. 11, 2009