Synthesis of a biferrocene diphosphine ligand with only planar chirality and its application in the Rh-catalyzed asymmetric hydrogenation of β-keto sulfones

Article abstract of DOI:10.1016/j.tetasy.2007.01.009

A new type of biferrocene diphosphine ligand bearing only planar chirality was developed and used in Rh(I)-catalyzed asymmetric hydrogenation of β-keto sulfones, giving the corresponding optically active β-hydroxy sulfones in excellent yields and in 72.4-

Full text of DOI:10.1016/j.tetasy.2007.01.009

Tetrahedron: Asymmetry 18 (2007) 224–228
Synthesis of a biferrocene diphosphine ligand with only
planar chirality and its application in the Rh-catalyzed
asymmetric hydrogenation of b-keto sulfones
*
*
Hui-Li Zhang, Xue-Long Hou, Li-Xin Dai and Zhi-Bin Luo
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
3
54 Fenglin Road, Shanghai 200032, China
Received 30 November 2006; accepted 9 January 2007
Abstract—A new type of biferrocene diphosphine ligand bearing only planar chirality was developed and used in Rh(I)-catalyzed asym-
metric hydrogenation of b-keto sulfones, giving the corresponding optically active b-hydroxy sulfones in excellent yields and in 72.4–
9
7.9% ee.
ꢀ
2007 Elsevier Ltd. All rights reserved.
1
. Introduction
and his co-workers has been proven to be very efficient in
1
3h
enantioselective hydrogenation.
During studies on the
1
4
Optically active b-hydroxy sulfones are useful chiral syn-
applications of ferrocene ligands in asymmetric catalysis,
thons for the synthesis of biologically active molecules such
we synthesized a biferrocene diphosphine ligand and used
it successfully in the Rh-catalyzed asymmetric hydrogena-
tion of b-keto sulfones. We reported herein this Rh-cata-
lyzed enantioselective hydrogenation of b-keto sulfones
using a bisferrocenyl diphosphine ligand (R,R)-5 with only
1
1,2
as c-butenolides, c-butyrolactones, 2,5-disubstituted tet-
3
4
rahydrofuran, and d-valerolactones. Many methods have
been developed so far for the preparation of optically
active b-hydroxy sulfones, such as kinetic resolution of
5
12a,c,15
racemic b-hydroxy sulfones and asymmetric reduction of
planar chirality.
b-keto sulfones, including baker’s yeast-mediated reduc-
6
7
tion. CBS catalyzed borane reduction, and NaBH /Me -
4
3
SiCl catalyzed reduction using polymer-supported chiral
sulfonamide as a ligand. Although asymmetric hydrogena-
2. Synthesis of ligand (R,R)-5
8
tion of the C@X bond has been one of the most important
From the readily available (S)-p-tolylsulfinylferrocene 1,16
9
reaction in asymmetric catalysis, there are a few reports on
compound (S ,S )-2 was synthesized according to the lit-
Fc
S
the metal catalyzed asymmetric hydrogenation of b-keto
erature with enantiomeric purity of over 99% ee after
1
,10
sulfones.
On the other hand, since the pioneering work
recrystallization using a chiral sulfoxide as an ortho-direct-
of Hayashi and Kumada in 1974 on the synthesis of the
16
ing group. Treatment of (S ,S )-2 with t-BuLi at
Fc
S
1
1
first chiral ferrocenyl phosphine, the planar chiral 1,2-
disubstituted ferrocene unit has become one of the most
useful backbones in the design of new ligands for asymmet-
ꢀ
78 ꢁC, followed by the addition of DMF provided phos-
17
phino-formyl ferrocene (R)-3. The reaction of (R)-3 with
lithiated (S ,S )-2 in THF at ꢀ78 ꢁC afforded biferrocene
Fc
S
1
2
ric catalysis. Recently, many ligands with the biferrocene
methanol (R,R)-4, subsequent removal of the borane on
phosphine by treating with DABCO in toluene at 60 ꢁC
provided target ligand (R,R)-5 (Scheme 1). It is noteworthy
that ligand (R,R)-5 bears only planar chirality on each fer-
rocene skeleton. It is stable, and no change was found from
NMR after exposing it in air for several months, albeit it is
unstable under acidic conditions.
1
3
structure have been synthesized, some of which were ap-
plied to the asymmetric hydrogenation reactions. Among
them, the diphosphine ligand PhTRAP developed by Ito
*
0
Corresponding authors. E-mail: xlhou@mail.sioc.ac.cn
957-4166/$ - see front matter ꢀ 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2007.01.009

H.-L. Zhang et al. / Tetrahedron: Asymmetry 18 (2007) 224–228
225
BH3
O
BH3
O
S
Ph2P
Ph P
2
S
CHO
a
b
Fe
Fe
Fe
(
S)-1
(SFc,SS)-2
(R)-3
BH3
BH3
OH
O
S
Ph2P
2
Ph P
OH
2
Ph P
c
d
Fe
Fe Ph P Fe
2
Ph P
2
Fe
Fe
BH3
(
SFc,SS)-2
(R,R)-4
(
R,R)-5
Scheme 1. Synthesis of biferrocene ligand (R,R)-5. Reagents and conditions: (a) (1) LDA, THF, ꢀ78 ꢁC; (2) PPh
2
Cl, ꢀ78 ꢁC; (3) BH
3
ÆMe
2
S, ꢀ78 ꢁC to rt,
6
5%; (b) (1) t-BuLi, THF, ꢀ78 ꢁC; (2) DMF, ꢀ78 ꢁC, 44%; (c) (1) t-BuLi, THF, ꢀ78 ꢁC; (2) (R)-3, ꢀ78 to 0 ꢁC; (d) DABCO, toluene, 60 ꢁC, 89% (c+d).
3
. Results and discussion
other hand, when there was an electron-withdrawing group
on the aromatic ring, slightly higher enantioselectivities
were obtained (entries 7, 8, 9, 10 vs entry 2). These results
showed that the electron density of the aromatic ring has
some effect on the enantioselectivity of the reduction, but
the reason is still obscure at the moment.
The reaction of Rh(COD) SbF with (R,R)-5 formed a Rh
2
6
complex, which was used as a catalyst in the asymmetric
hydrogenation of b-keto sulfones 1–8 (Eq. 1, Table 1).
Thus, treatment of 2-(phenylsulfonyl)acetophenone 1 with
hydrogen (20 bar, 50 ꢁC, 18 h) in the presence of
Rh(COD) SbF (1 mol %) and ligand (R,R)-5 (1.1 mol %)
2
6
in methanol led to b-hydroxy sulfone 9 in almost quantita-
tive yield and with moderate enantioselectivity (entry 1).
H2 (85 bar)
Rh(COD)2SbF6 (1 mol%)
O
OH
* Ar
5
(
R,R)-5 (1.1 mol%)
When raising the H pressure to 85 bar in isopropanol,
2
PhSO2
PhSO2
Ar
iPrOH, 40 °C
the product was obtained in quantitative yield with much
higher enantioselectivity (95.6% ee, entry 2). However, rais-
ing the reaction temperature from 40 to 60 ꢁC led to a drop
of enantioselectivity from 95.6% to 91.2% ee (entry 3 vs en-
try 2).
1 Ar=C H
6
5
9 Ar=C H
6
2 Ar=p-Me-C6H4
10 Ar=p-Me-C6H4
11 Ar=o-Me-C6H4
12 Ar=p-MeO-C6H4
13 Ar=p-Cl-C6H4
14 Ar=m-Cl-C6H4
15 Ar=p-F-C6H4
16 Ar=p-Br-C6H4
ð1Þ
3
4
5
6
Ar=o-Me-C6H4
Ar=p-MeO-C6H4
Ar=p-Cl-C6H4
Ar=m-Cl-C6H4
When the optimized reaction condition (85 bar H , 40 ꢁC
7 Ar=p-F-C6H4
2
8
Ar=p-Br-C6H4
in isopropanol) was applied to other b-keto sulfones 2–8
with different substituents on the aromatic ring of the Ph
group, enantioselectivities ranging from 72.4% to 97.9%
ee were obtained with excellent conversion. When the sub-
stituent on the aromatic ring was an electron-donating
group (e.g., p-methyl, p-methoxy, o-methyl), lower enantio-
selectivities were obtained (entries 4, 5, 6 vs entry 2). On the
4. Conclusion
We have developed a novel biferrocene diphosphine ligand
with only planar chirality. When it was applied in the
a
Table 1. Rhodium-catalyzed hydrogenation of b-keto sulfones
b
c
Entry
Substrate
Solvent
H
2
(bar)
Time (h)
T (ꢁC)
Conv (%)
ee (%)
1
2
3
4
5
6
7
8
9
1
1
1
2
3
4
5
6
7
8
MeOH
20
85
85
85
85
85
85
85
85
85
18
24
12
12
12
12
12
12
12
12
50
40
60
40
40
40
40
40
40
40
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
56
i
PrOH
95.6
91.4
91.2
72.4
82.9
97.9
97.1
96.0
97.0
i
PrOH
i
PrOH
i
PrOH
i
PrOH
i
PrOH
i
PrOH
i
PrOH
i
1
0
PrOH
a
b
c
Reaction and conditions: Rh(COD)
Determined by H NMR.
Ee was determined by HPLC.
2
SbF
6
/(R,R)-5/sub = 1/1.1/100.
1

226
H.-L. Zhang et al. / Tetrahedron: Asymmetry 18 (2007) 224–228
rhodium-catalyzed enantioselective hydrogenation of
b-keto sulfones, high enantioselectivities and nearly quanti-
tative conversions were achieved. Further modification of
the ligand and application in asymmetric catalysis are in
progress.
the crude product was purified by basic Al O column
2 3
chromatography (elution: petroleum ether/EtOAc 50/1)
to give 830 mg of the product (R,R)-5 as a yellow solid.
2
0
Yield: 89%. Mp 190–192 ꢁC; ½aꢁ ¼ þ400 ðc 0:215;
D
1
CHCl Þ; H NMR (300 MHz, CDCl ): d 3.48 (s, 1H),
3
3
3
4
.51 (s, 1H), 3.59–3.66 (m, 3H), 4.01 (s, 5H), 4.03 (s, 5H),
.16 (s, 1H), 4.28 (s, 1H), 5.60–5.63 (m, 1H), 6.92–7.55
1
3
5. Experimental
(m, 20H); C NMR (75 MHz, CDCl ): d 139.66, 139.56,
3
1
39.18, 139.10, 137.19, 137.10, 137.02, 136.93, 135.41,
135.32, 135.13, 135.04, 132.56, 132.54, 132.34, 132.31,
29.15, 129.05, 128.01, 127.98, 127.91, 127.87, 127.57,
5
.1. General
All NMR spectra were measured in CDCl using a Bruker
1
127.52, 127.46, 127.43, 98.09, 97.89, 97.77, 97.60, 73.87,
73.80, 72.78, 73.70, 72.65, 72.55, 71.66, 71.60, 70.97,
70.91, 70.32, 70.12, 69.99, 69.69, 69.57, 69.46, 69.06,
3
1
13
AMX-300 instrument [300 MHz ( H), 75 MHz ( C),
1
3
1
21.46 MHz ( P)], and chemical shifts are expressed in
3
1
parts per million relative to internal CHCl (7.26 ppm for
69.00, 68.92, 68.89, 68.75, 68.48; P NMR (121.46 MHz,
3
1
13
H, 77.0 ppm for C, and 85% H PO as the external ref-
CDCl ): d ꢀ26.37, ꢀ28.20; MS (MALDI) m/z (rel) 767
3
4
3
3
1
+
+
erence for P). IR spectrum was recorded on a Shimadzu
IR-400 using KBr pellets. All manipulations involving air-
sensitive reagents were carried out under an argon atmo-
sphere. The hydrogenation reactions were performed in a
(M ꢀH), 769 (M +H); IR (KBr) 1712 (w), 1478 (w),
1433 (w), 695 (m); HRMS (ESI): calcd for C H OFe P
2 2
4
5
38
+
[M +H] 769.1182, found: 769.1169.
3
00 mL stainless steel autoclave. All solvents were treated
5.2. General procedure for the asymmetric hydrogenation of
b-keto sulfones
using standard procedures before use.
5
.1.1. Preparation of (R)-3. To a solution of (S ,S )-2
To a 10 mL tube were added Rh(COD) SbF6 (2.8 mg,
Fc
S
2
(
3 g, 5.75 mmol) in THF (60 mL) was added dropwise
tert-BuLi (4.2 mL, 6.3 mmol, 1.5 M in pentane) at
78 ꢁC during 10 min, and the resulting red-orange solu-
tion was stirred at ꢀ78 ꢁC for 10 min before addition of
mL DMF (65 mmol). After stirring at the same tempera-
ture for 2 h, the light colored solution was quenched with
0 mL of water. The aqueous layer was extracted with
CH Cl (10 mL · 2), and the combined organic phase
0.005 mmol) and (R,R)-5 (4.3 mg, 0.0055 mmol). The tube
was then transferred into a dry box in a dry nitrogen atmo-
sphere and the mixture was dissolved in degassed isopropa-
nol (2 mL). After the reaction mixture was stirred for
30 min at room temperature, keto sulfone (0.5 mmol) was
added. The reaction was carried out in an autoclave at
the desired hydrogen pressure and temperature for a
designated period of time. After removal of the solvent,
the residue was purified by silica gel chromatography to af-
ford the b-hydroxysulfone (over 99% conversion of b-keto
ꢀ
5
2
2
2
was dried over Na SO , concentrated, and purified by silica
gel column chromatography (elution: petroleum ether/
EtOAc/CH Cl 20/5/2). The product was then recrystal-
2
4
1
sulfones were obtained in all reactions indicated by H
2
2
lized at ꢀ20 ꢁC to give 1.0 g of (R)-3 as red crystals,
NMR).
2
D
0
Yield: 44%. Mp 140–142 ꢁC; ½aꢁ ¼ ꢀ556 ðc 0:2;
1
1
CHCl
3
Þ; H NMR (300 MHz, CDCl ): d 1.5 (br, 3H),
5.2.1. 1-Phenyl-2-(phenylsulfonyl)ethanol 9. H NMR
(300 MHz, CDCl ): d (ppm) 3.30 (dd, J = 1.8, 14.4 Hz,
1H), 3.50 (dd, J = 10.2, 14.4 Hz, 1H), 3.75 (s, 1H), 5.26
(d, J = 9.6 Hz, 1H), 7.28–7.95 (m, 10H). HPLC (Chiralpak
AD-H) elution with i-PrOH/hexane = 30/70, flow rate:
1.0 mL/min, k = 254 nm, retention times: t 11.25 min, t
3
4
7
.26 (m, 1H), 4.40 (s, 5H), 4.83 (br, 1H), 5.26 (br, 1H),
.35–7.70 (m, 10H), 10.24 (s, 1H); MS (EI) m/z (rel) 412
M , 5.94), 398 (100), 369 (38), 399 (27), 332 (24), 183
3
+
(
(
23), 370 (22), 304 (20), 170 (18); IR (KBr) 2392 (w),
3
1
1
664 (s), 1437 (w), 1410 (w), 1247 (w);
11.63 (m); Anal. Calcd
for C H BPOFe: C, 67.04; H, 5.38; Found: C, 66.85;
P NMR
1
2
(
121.46 MHz, CDCl3):
d
13.38 min.
2
3
22
0
H, 5.29.
.1.2. Preparation of (R,R)-5. To a solution of (S ,S )-2
5.2.2. 1-(4 -Methylphenyl)-2-(phenylsulfonyl)ethanol 10.
1
H NMR (300 MHz, CDCl ): d (ppm) 2.31 (s, 3H), 3.32
3
5
(dd, J = 2.1, 15 Hz, 1H), 3.50 (dd, J = 9.6, 14.1 Hz, 1H),
3.63 (d, J = 2.7 Hz, 1H), 5.23 (d, J = 9.6 Hz, 1H), 7.10–
7.18 (m, 4H), 7.55–7.71 (m, 3H), 7.94–7.96 (m, 2H). HPLC
(Chiralpak AD-H) elution with i-PrOH/hexane = 40/60,
flow rate: 0.3 mL/min, k = 254 nm, retention times: t1
Fc
S
(
783 mg, 1.55 mmol) in dry THF (30 mL) was added drop-
wise tert-BuLi (4.2 mL, 6.3 mmol, 1.5 M in pentane) at
78 ꢁC during 10 min, and the resulting red-orange solu-
tion was stirred at ꢀ78 ꢁC for 10 min. Then a solution of
R)-3 (487 mg, 1.22 mmol) in dry THF (15 mL) was added
ꢀ
(
35.04 min, t 38.75 min.
2
dropwise. After stirring at the same temperature for 1 h,
the light yellow solution was quenched with 10 mL of water
at 0 ꢁC. The aqueous layer was extracted with EtOAc
0
5.2.3. 1-(2 -Methylphenyl)-2-(phenylsulfonyl)ethanol 11.
H NMR (300 MHz, CDCl ): d (ppm) 2.06 (s, 3H), 3.24
1
3
(
10 mL · 2), and the combined organic phases were dried
(dd, J = 1.2, 14.4 Hz, 1H), 3.43 (dd, J = 9.6, 14.7 Hz,
1H), 3.67 (d, J = 1.5 Hz, 1H), 5.43 (d, J = 8.1 Hz, 1H),
7.06–7.23 (m, 3H), 7.47–7.73 (m, 4H), 7.96–8.00 (m, 2H).
HPLC (Chiralpak AD-H) elution with i-PrOH/hex-
ane = 40/60, flow rate: 0.6 mL/min, k = 254 nm, retention
times: t 15.51 min, t 17.92 min.
over anhydrous Na SO , concentrated. The crude product
2
4
was dissolved in 20 mL of toluene, and DABCO (1.8 g,
.18 mmol) was added. The reaction mixture was stirred
8
for 4 h at 60 ꢁC. After the reaction mixture was cooled to
about 30 ꢁC, toluene was removed under reduced pressure,
1
2

H.-L. Zhang et al. / Tetrahedron: Asymmetry 18 (2007) 224–228
227
0
5
.2.4. 1-(4 -Methoxyphenyl)-2-(phenylsulfonyl)ethanol 12.
3. Tanikaga, R.; Hosoya, K.; Kaji, A. J. Chem. Soc., Perkin
Trans. 1 1987, 1799.
1
H NMR (300 MHz, CDCl ): d (ppm) 3.30 (dd, J = 1.8,
6.8 Hz, 1H), 3.50 (dd, J = 10.2, 14.4 Hz, 1H), 3.63 (d,
J = 1.8 Hz, 1H), 3.76 (s, 3H), 5.22 (br, 1H), 6.80–6.85 (m,
H), 7.17–7.22 (m, 2H), 7.55–7.92 (m, 3H), 7.92–7.96 (m,
H). HPLC (Chiralpak OJ-H) elution with i-PrOH/hex-
ane = 40/60, flow rate: 0.6 mL/min, k = 254 nm, retention
times: t 40.75 min, t 51.23 min.
3
4
5
6
. Kozikowski, A. P.; Mugrage, B. B.; Li, C. S.; Felder, L.
Tetrahedron Lett. 1986, 27, 4817.
. Chinchilla, R.; N a´ jera, C.; Pardo, J.; Yus, M. Tetrahedron:
Asymmetry 1990, 1, 571.
. (a) Gotor, V.; Rebollelo, F.; Liz, R. Tetrahedron: Asymmetry
1
2
2
2
001, 12, 513; (b) Roberts, S. M. J. Chem. Soc., Perkin Trans.
1
2
1 1999, 1; (c) Csuk, R.; Glanzer, B. I. Chem. Rev. 1991, 91, 49.
. Cho, B. T.; Kim, D. J. Tetrahedron: Asymmetry 2001, 12,
2043.
7
0
.2.5. 1-(4 -Chlorophenyl)-2-(phenylsulfonyl)ethanol 13.
H NMR (300 MHz, CDCl ): d (ppm) 3.30 (dd, J = 1.8,
4.1 Hz, 1H), 3.46 (dd, J = 9.9, 14.4 Hz, 1H), 3.79 (d,
J = 2.1 Hz, 1H), 5.26 (d, J = 7.5 Hz, 1H), 7.21–7.30 (m,
H), 7.57–7.72 (m, 3H), 7.93–7.96 (m, 2H). HPLC (Chir-
alpak OJ-H) elution with i-PrOH/hexane = 40/60, flow
rate: 0.8 mL/min, k = 254 nm, retention times: t1
5
1
8. Zhao, G.; Hu, J. B.; Qian, Z. S.; Yin, W. X. Tetrahedron:
Asymmetry 2002, 13, 2095.
3
1
9
. For some recent reviews on asymmetric hydrogenation: (a)
Ding, K.; Wang, Z.; Wang, X.; Liang, Y.; Wang, X. Chem.
Eur. J. 2006, 12, 5188; (b) Jaekel, C.; Paciello, R. Chem. Rev.
4
2
2
006, 106, 2912; (c) Wu, J.; Chan, A. S. C. Acc. Chem. Res.
006, 39, 711; (d) Xie, J.; Zhu, S.; Fu, Y.; Hu, A.; Zhou, Q.
2
0.02 min, t 21.87 min.
2
Pure Appl. Chem. 2005, 77, 2121; (e) Tang, W.; Zhang, X.
Chem. Rev. 2003, 103, 3029; (f) Crepy, K. V. L.; Imamoto, T.
Adv. Synth. Catal. 2003, 345, 79; (g) Noyori, R. Angew.
Chem., Int. Ed. 2002, 41, 2008; (h) Knowles, W. S. Angew.
Chem., Int. Ed. 2002, 41, 1998; (i) Brown, J. M. In
Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz,
A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Vol. 1, p
0
5
.2.6. 1-(3 -Chlorophenyl)-2-(phenylsulfonyl)ethanol 14.
1
H NMR (300 MHz, CDCl ): d (ppm) 3.31 (dd, J = 1.8,
3.5 Hz, 1H), 3.46 (dd, J = 9.3, 14.1 Hz, 1H), 3.84 (d,
J = 2.4 Hz, 1H), 5.25 (d, J = 6.9 Hz, 1H), 7.14–7.30 (m,
H), 7.56–7.72 (m, 3H), 7.92–7.95 (m, 2H). HPLC (Chir-
alpak AD-H) elution with i-PrOH/hexane = 30/70, flow
rate: 0.6 mL/min, k = 254 nm, retention times: t1
4.96 min, t 18.09 min.
3
1
4
1
21.
1
0. Bertus, R.; Phansavath, P.; Rotovelomanana-Vidal, V.;
Gen eˆ t, J. P.; Touati, A. R.; Hornri, T.; Ben Halsine, B.
Tetrahedron Lett. 1999, 40, 3175.
1
2
1
1. (a) Hayashi, T.; Yamamoto, K.; Kumada, M. Tetrahedron
Lett. 1974, 15, 4405; (b) Hayashi, T.; Mise, T.; Fukushima,
M.; Kagotani, M.; Nagashima, N.; Hamada, Y.; Matsumoto,
A.; Kawakami, S.; Konishi, M.; Yamamoto, K.; Kumada,
M. Bull. Chem. Soc. Jpn. 1980, 53, 1138; (c) Hayashi, T.;
Konishi, M.; Fukushima, M.; Mise, T.; Kagotani, M.; Tajika,
M.; Kumada, M. J. Am. Chem. Soc. 1982, 104, 180.
0
1
5
.2.7. 1-(4 -Flurophenyl)-2-(phenylsulfonyl)ethanol 15.
H
NMR (300 MHz, CDCl ): d (ppm) 3.30 (dd, J = 2.1,
3
1
1
7
3.8 Hz, 1H), 3.47 (dd, J = 9.3, 13.8 Hz 1H), 3.79 (s,
H), 5.26 (d, J = 9.9 Hz, 1H), 6.96–7.01 (m, 2H), 7.24–
.28 (m, 2H), 7.56–7.71 (m, 3H), 7.92–7.95 (m, 2H). HPLC
Chiralpak AD-H) elution with i-PrOH/hexane = 30/70,
flow rate: 0.6 mL/min, k = 254 nm, retention times: t1
(
1
2. For some reviews: (a) Array a´ s, R. G.; Adrio, J.; Carretero, J.
C. Angew. Chem., Int. Ed. 2006, 45, 7674; (b) Dai, L.-X.; Tu,
T.; You, S.-L.; Deng, W.-P.; Hou, X.-L. Acc. Chem. Res.
1
9.45 min, t 21.67 min.
2
2
003, 36, 659; (c) Atkinson, R. C. J.; Gibson, V. C.; Long, N.
0
5
.2.8. 1-(4 -Bromophenyl)-2-(phenylsulfonyl)ethanol 16.
J. Chem. Soc. Rev. 2004, 33, 313; (d) Sutcliffe, O. B.; Bryce,
M. R. Tetrahedron: Asymmetry 2003, 14, 2297; (e) Colacot, T.
J. Chem. Rev. 2003, 103, 3101; (f) Togni, A. In Metallocenes;
Togni, A, Halterman, R. L., Eds.; Wiley-VCH: Weinheim,
Germany, 1998; Vol. 2, Chapter 10; (g) Richards, C. J.;
Locke, A. J. Tetrahedron: Asymmetry 1998, 9, 2377; (h)
Hayashi, T. In Ferrocenes; Togni, A., Hayashi, T., Eds.;
VCH: Weinheim, Gemany, 1995, Chapter 2.
1
H NMR (300 MHz, CDCl ): d (ppm) 3.30 (dd, J = 2.4,
4.7 Hz, 1H), 3.46 (dd, J = 9.6, 14.1 Hz 1H), 3.81 (d,
J = 1.8, 1H), 5.25 (dd, J = 2.4 and 9.6 Hz, 1H), 7.15–7.19
m, 2H), 7.42–7.46 (m, 2H), 7.57–7.73 (m, 3H), 7.93–7.95
m, 2H). HPLC (Chiralpak OJ-H) elution with i-PrOH/
hexane = 40/60, flow rate: 0.6 mL/min, k = 254 nm, reten-
tion times: t 29.71 min, t 33.07 min.
3
1
(
(
1
2
1
3. For some examples: (a) Fukuzawa, S.; Yahara, Y.; Kami-
yama, A.; Hara, M.; Kikuchi, S. Org. Lett. 2005, 7, 5809; (b)
Gischig, S.; Togni, A. Organometallics 2004, 23, 2479; (c)
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Organometallics 2004, 23, 1991; (d) Dai, H.-C.; Hu, X.-P.;
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Acknowledgments
We are grateful for financial support from the National
Natural Sciences Foundation of China, the Major Basic
Research Development Program, Chinese Academy of Sci-
ences, and Science and Technology Commission of Shang-
hai Municipality.
(
e) Fadini, L.; Togni, A. Chem. Commun. 2003, 30; (f)
Shintani, R.; Fu, G. C. Angew. Chem., Int. Ed. 2003, 42, 4082;
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(
2
Karube, D.; Ito, Y. J. Am. Chem. Soc. 2000, 122, 7614; (i)
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3