π-Allylic sulfonylation in water with amphiphilic resin-supported palladium-phosphine complexes

Article abstract of DOI:10.1055/s-2008-1067096

π-Allylic substitution of allyl esters with sodium arylsul-finate was performed with an amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported phosphine-palladium complex in water as a single reaction medium under heterogeneous conditions to give allyl sulfones in good to high yields. Catalytic asymmetric allylic substitution of cycloalkenyl esters also took place in water using a PS-PEG resin-supported chiral imidazo-indolephosphine- palladium complex to give cycloalkenyl sulfones with up to 81% ee.

Full text of DOI:10.1055/s-2008-1067096

1960
SPECIAL TOPIC
p-Allylic Sulfonylation in Water with Amphiphilic Resin-Supported
Palladium–Phosphine Complexes
P
alladium-Catalyz
a
e
d
p
-Allyli
s
c
S
ulfonyl
u
ation in
W
at
h
er iro Uozumi,* Toshimasa Suzuka
Institute for Molecular Science (IMS) and CREST, Higashiyama 5-1, Myodaiji, Okazaki 444-8787, Japan
Fax +81(564)595574; E-mail: uo@ims.ac.jp
Received 1 January 2008
Abstract: p-Allylic substitution of allyl esters with sodium arylsul-
Pd
X
SO2Ph
Pd
finate was performed with an amphiphilic polystyrene-poly(ethyl-
ene glycol) (PS-PEG) resin-supported phosphine-palladium
complex in water as a single reaction medium under heterogeneous
conditions to give allyl sulfones in good to high yields. Catalytic
asymmetric allylic substitution of cycloalkenyl esters also took
place in water using a PS-PEG resin-supported chiral imidazo-
indolephosphine-palladium complex to give cycloalkenyl sulfones
with up to 81% ee.
R
R'
R
R'
R
(R')
R'
(R)
NaSO2Ph
in H2O
O
C
Ph2
P
Pd
PS
O
O
N
H
n
Pd
1
Key words: p-allylpalladium, sulfone, aqueous media, polymer
support, palladium catalyst
Cl
Scheme 1 p-Allylic sulfonylation
The palladium-catalyzed allylic substitution reaction, the
Tsuji–Trost reaction, has been recognized as one of the
most powerful carbon–carbon and carbon–nitrogen bond-
forming reactions in use today. However, in spite of the
widespread synthetic utility of allyl sulfones,1,2 the well-
developed research on p-allylic sulfonylation has been
limited to isolated reports.3–5 One of the major problems
associated with the p-allylic sulfonylation lies in the low
solubility of the sulfone nucleophiles, for example, sodi-
um sulfinates, in organic solvents. We have recently de-
veloped amphiphilic polystyrene-poly(ethylene glycol)
(PS-PEG) resin-supported phosphine–palladium com-
plexes which promote various catalytic transformations,6
including allylic substitution,7 smoothly in water8 under
heterogeneous conditions9,10 to meet the requirements of
safe, green, and high-throughput chemical processes. Our
continuing interest in the aquacatalytic utility of PS-PEG
resin-supported palladium complexes led us to examine
the p-allylic sulfonylation in water with the PS-PEG-Pd
complexes.11 We report herein a heterogeneous aquacata-
lytic p-allylic substitution of various allyl esters with so-
dium arylsulfinate (Scheme 1), and also describe our
preliminary studies on the asymmetric p-allylic sulfonyla-
tion of cycloalkenyl esters (up to 81% ee) (Scheme 2).12
Pd*
Y
Y
SO2Ph
NaSO2Ph
in H2O
X
X
X
racemic
O
H
O
PS
O
O
N
H
C
(CH2)3
N
n
N
+
Cl–
Pd
P
Ph2
resin-supported PdL*
Pd*
6
Scheme 2 Asymmetric p-allylic sulfonylation
cinnamyl phenyl sulfone (3a) (Table 1, entry 1). A range
of acyclic and cyclic carbonates of the corresponding pri-
mary, secondary, and tertiary allylic alcohols were readily
sulfonylated under similar conditions. Representative re-
sults are summarized in Table 1. The carbonate ester 2b,
the allylic isomer of cinnamyl carbonate 2a, gave exclu-
sively cinnamyl phenyl sulfone 3a (entry 2), when the
same procedure for entry 1 was employed, in which the
isomeric sulfone 3b (Figure 1) was not detected on GC.
The sulfonylation of the aryl vinyl carbinol esters 2c and
2d bearing electron-donating and -withdrawing substitu-
ents at their para positions gave the cinnamyl sulfones 3c
and 3d in 84 and 83% yield, respectively (entries 3 and 4).
The reaction of methyl cinnamyl carbonate (2a) with so-
dium benzenesulfinate was carried out in water at 25 °C
for 12 hours in the presence of 5 mol% palladium of the
PS-PEG (TentaGel)13 resin-supported p-allylpalladium–
triarylphosphine complex 1.
The diphenylpropenyl ester 2e also underwent sulfonyla-
tion to give 3e in 90% yield (entry 5). Geranyl, neryl, and
linalyl carbonates 2f, 2g, and 2h reacted with sodium sul-
finate under similar conditions to give 62, 78, and 89%
yield, respectively, of a mixture of regioisomeric sulfony-
lation products 3f and 3h (entries 6, 7, and 8). The ratios
of the geranyl sulfone 3f and the linalyl sulfone 3h ob-
tained from the reactions of 2f, 2g, and 2h were almost the
The catalyst resin beads were filtered off and extracted
with a small portion of ethyl acetate to give 86% yield of
SYNTHESIS 2008, No. 12, pp 1960–1964
x
x.
x
x
.
2
0
0
8
Advanced online publication: 16.05.2008
DOI: 10.1055/s-2008-1067096; Art ID: C00108SS
© Georg Thieme Verlag Stuttgart · New York

SPECIAL TOPIC
Palladium-Catalyzed p-Allylic Sulfonylation in Water
1961
Table 1 p-Allylic Sulfonylation of Allyl Carbonates 2 in H2Oa
same (3f/3h = 1:9); the neryl sulfone 3g (Figure 1) was
not observed at all. These results demonstrate that the re-
actions of 2f–h proceeded by way of the same p-allylpal-
ladium intermediate. The cyclic substrates 2i, 2j, and 2k
also underwent p-allylic sulfonylation to afford the corre-
sponding sulfones 3i, 3j, and 3k in 80, 84, and 86% isolat-
ed yield, respectively. The sulfonylation of cis-5-
methoxycarbonylcyclohex-2-enyl methyl carbonate (4)
was also catalyzed by the PS-PEG palladium 1 in water at
25 °C to afford the cis-5-methoxycarbonylcyclohex-2-
enyl phenyl sulfone (5) in 87% yield (Scheme 3). The ex-
clusive formation of the cycloalkenyl sulfone 5 having the
cis-configuration from the cis-allylic ester 4 revealed that
this p-allylic sulfonylation proceeds via a double-inver-
sion pathway (p-allylpalladium formation and nucleo-
philic attack with a sulfinate anion) in water under these
conditions.
Entry Allyl ester 2
Product 3
Yield
(%)
OCOOMe
SO2Ph
1
86
84
3a
3a
2a
OCOOMe
2
3
2b
OCOOMe
SO2Ph
84
F3C
F3C
3c
2c
OCOOMe
SO2Ph
SO2Ph
4
5
83
90
MeO
MeO
3d
2d
SO2Ph
SO2Ph
OCOMe
3b
3g
Figure 1
2e
2f
3e
Pd
1
(1 mol% Pd)
OCOOMe
SO2Ph
OCOOMe
SO2Ph
SO2Ph
6
62
NaSO2Ph (1.5 equiv)
25 °C, 12 h, in H2O
COOMe
COOMe
5 (87%)
3f
(11:89)
3h
4
PS-
Pd
PEG
–SO2Ph
COOMe
7
3f/3h (11:89)
78
89
OCOOMe
2g
Scheme 3
Recycling experiments were examined for sulfonylation
of the diphenylpropenyl ester 2e. After the first use of the
polymeric palladium catalyst 1 (Table 1, entry 5) to give
87% yield of the adduct 3e, the recovered catalyst beads
were taken on to two reuses and exhibited stable catalytic
activity (Scheme 4).
OCOOMe
8
9
3f/3h (11:89)
2h
OCOOMe
SO2Ph
80
84
Pd
2i
2j
3i
(5 mol% Pd)
1
1st use: 89% yield
2nd us: 87% yield
3rd use: 90% yield
SO2Ph
OCOOMe
3e
2e
NaSO2Ph
(2e/NaSO2Ph = 3:2)
25 °C, 12 h, in H2O
10
11
3j
Scheme 4 Recycling experiments
OCOOMe
SO2Ph
Using this p-allylic sulfonylation protocol, we examined
next the catalytic asymmetric sulfonylation in water with
an amphiphilic PS-PEG resin-supported chiral palladium
complex.14,15 We previously reported the heterogeneous
86
2k
3k
a All reactions were carried out in H2O at 25 °C for 12 h. The ratio of
2 (mol)/NaSO2Ph (mol)/Pd (mol)/H2O (L) = 1:1.5:0.05:2.
Synthesis 2008, No. 12, 1960–1964 © Thieme Stuttgart · New York

1962
Y. Uozumi, T. Suzuka
SPECIAL TOPIC
ized with a Millipore system as Milli-Q grade. NMR spectra were
Pd*
6
1
recorded on a JEOL JNM-AL400 spectrometer (400 MHz for H,
SO2Ph
Y
Y
100 MHz for 13C) or a JEOL JNM-LA500 spectrometer (500 MHz
for 1H, 125 MHz for 13C). 1H and 13C NMR spectra were recorded
in CDCl3 at 25 °C. Chemical shifts were reported in ppm referenced
+
NaSO2Ph
in H2O
X
X
X
1
racemic
rac-2i–k
to an internal tetramethylsilane standard for H NMR. Chemical
shifts of 13C NMR were given relative to CDCl3 as an internal stan-
dard (d = 77.0 ppm). The mass spectral data were measured on an
Agilent 6890 GC/5973N MS detector (GC-MS) and JEOL JMS-
700 (EI-MS); the abbreviation ‘bp’ is used to denote the base peak.
IR analysis was performed on a JASCO FTIR-460. Optical rota-
tions were measured on a JASCO P-1020 polarimeter. HPLC anal-
ysis was performed on a JASCO PU-1580 liquid chromatograph
system. PS-PEG-supported catalysts were prepared from PS-PEG
amino-resin (TentaGelS NH2, average diameter 0.90 µm, 1% divi-
nylbenzene cross-linked, loading value of amino residue 0.31
mmol/g; purchased from RAPP POLYMERETM) according to the
3i–k
(S)-3i: X = none; 25 °C, 1 h; 80% yield, 45% ee
(S)-3j: X = CH2; 25 °C, 1 h; 78% yield, 33% ee
1 h;
12 h;
0.5 h;
(S)-3k: X = CH2CH2; 25 °C,
84% yield, 71% ee
83% yield, 10% ee
52% yield, 81% ee
25 °C,
0 °C,
Scheme 5 Asymmetric substitution in H2O
aquacatalytic chiral process by catalytic asymmetric p-al-
lylic alkylation and amination of cycloalkenyl esters using
a palladium catalyst coordinated with a novel optically ac-
tive ligand, (3R,9aS)-[2-aryl-3-(2-diphenylphosphino)phe- reported procedure.7b,12c
nyl]tetrahydro-1H-imidazo[1,5-a]indol-1-one, anchored
onto PS-PEG resin (Scheme 2, polymeric ligand 6). Pre-
liminary studies on the aquacatalytic asymmetric allylic
sulfonylation of cycloalkenyl esters was examined with
cycloheptenyl methyl carbonate 2k (Scheme 5). When a
mixture of the cycloheptenyl carbonate 2k and 1.5 equiv-
alents of sodium sulfinate in water was shaken at 25 °C
for 1 hour in the presence of the PS-PEG resin-supported
chiral palladium–imidazoindole phosphine 6 (5 mol%
palladium), the 3-(phenylsulfonyl)cyclohept-1-ene (3k)
was obtained in 84% yield. The enantiomeric purity of 3k
was determined by HPLC analysis [Chiralcel OD-H (500
mm), n-hexane–i-PrOH, 9:1] to be 71% ee, and the abso-
lute configuration was determined to be S by measure-
ment of the specific rotation ([a]D25 –145 (c 1.0, CH2Cl2)).
The cyclohexenyl and cyclopentenyl carbonates 2j and 2i
gave the corresponding cycloalkenyl sulfones 3j and 3i in
33 and 45% ee, respectively. The enantiomeric purity of
the sulfonylated product 3k decreased as the reaction time
was prolonged. Thus, the sulfonylation of 2k for 12 hours
gave only 10% ee of the product 3k under otherwise sim-
ilar reaction conditions, whereas 71% ee of 3k was ob-
tained in one hour. It has been reported that allyl sulfones
can react with dialkyl malonate derivatives under basic
conditions in the presence of a palladium(0) catalyst via p-
allylpalladium intermediates.16 During the asymmetric
sulfonylation of 2k, the enantiomerically enriched 3k gen-
erated in situ should undergo the p-allylpalladium forma-
tion and subsequent (nonproductive) sulfonylation to
result in the racemization of 3k. The highly enantiomeri-
cally enriched 3k of 81% ee was obtained when the asym-
metric sulfonylation of the cycloheptenyl carbonate 2k
was carried out at 0 °C for 30 minutes.
CAS Registry No.: 3a, 16212-07-0; 3d, 863310-91-2; 3e, 191542-
63-9; 3f, 56691-80-6; 3h, 91940-11-3; 3i, 140396-96-9; 3j, 87413-
32-9; 3k, 131179-47-0; 5, 74866-39-0.
Palladium-Catalyzed Allylic Substitution of Allyl Esters with
Sodium Benzenesulfinate; 3-(Phenylsulfonyl)-1-phenylpropene
(3a); Typical Procedure
To a mixture of the catalyst 1 (92 mg, 0.025 mmol) and cinnamyl
carbonate (2a; 96.0 mg, 0.5 mmol) in H2O (2.0 mL) was added so-
dium benzenesulfinate (150 mg, 0.75 mmol) and the mixture was
stirred at 25 °C for 12 h. The mixture was filtered and the recovered
resin beads were rinsed with EtOAc (3 mL). The EtOAc layer was
separated and the aqueous layer was extracted with EtOAc (5 mL).
The combined EtOAc extracts were washed with brine (2 mL) and
dried (MgSO4). The solvent was evaporated and the residue was
chromatographed on silica gel (hexane–EtOAc, 1:1) to give 110.8
mg (86%) of 3a (Table 1).
IR (ATR): 2982, 1237, 1086 cm–1.
1H NMR (CDCl3): d = 7.88 (d, J = 7.3 Hz, 2 H), 7.63 (t, J = 7.3 Hz,
1 H), 7.54 (t, J = 7.3 Hz, 2 H), 7.32–7.25 (m, 5 H), 6.36 (d, J = 15.8
Hz 1 H), 6.09 (td, J = 7.9, 15.8 Hz, 1 H), 3.95 (d, J = 7.9 Hz, 2 H).
13C NMR (CDCl3): d = 139.1 (2 C), 138.3, 135.6, 133.7, 129.0,
128.6 (4 C), 126.5, 115.0, 60.4.
MS (EI): m/z (%) = 258 (2, M+), 198 (7), 117 (bp), 77 (75).
3-(Phenylsulfonyl)-1-(4-trifluoromethylphenyl)propene (3c)
IR (ATR): 2925, 1302, 1084, 892 cm–1.
1H NMR (CDCl3): d = 7.88 (d, J = 7.3 Hz, 2 H), 7.66 (t, J = 7.3 Hz,
1 H), 7.55 (t, J = 7.3 Hz, 2 H), 7.54 (d, J = 8.3 Hz, 2 H), 7.38 (d,
J = 8.3 Hz, 2 H), 6.42 (d, J = 16.1 Hz, 1 H), 6.21 (td, J = 7.3, 16.1
Hz 1 H), 3.97 (d, J = 7.3 Hz, 2 H).
13C NMR (CDCl3): d = 139.0, 138.3, 137.7, 133.9, 130.3 (q,
J = 36.4 Hz), 129.1, 128.4, 126.7, 125.6 (q, J = 4.1 Hz), 123.9 (q,
J = 267.8 Hz), 117.9, 60.2.
MS (EI): m/z (%) = 307 (1, M+ – F), 165 (51), 115 (67), 77 (bp), 51
(58).
In summary, the palladium-catalyzed p-allylic sulfonyla-
tion was achieved with sodium benzenesulfinate in water Anal. Calcd for C16H13F3O2S: C, 58.89; H, 4.02. Found: C, 58.44;
H, 4.11.
with polymeric palladium complexes to meet safe and
green chemical requirements. Asymmetric p-allylic sulfo-
3-(Phenylsulfonyl)-1-(4-methoxyphenyl)propene (3d)
nylation of cycloalkenyl carbonates was also carried out
IR (ATR): 2983, 1606, 1509, 1249, 1135 cm–1.
1H NMR (CDCl3): d = 7.87 (d, J = 7.9 Hz, 2 H), 7.63 (t, J = 7.9 Hz,
1 H), 7.53 (t, J = 7.9 Hz, 1 H), 7.21 (d, J = 9.1 Hz, 2 H), 6.84 (d,
in water without any organic solvent to give up to 81% ee.
All manipulations were carried out under a nitrogen atmosphere.
Nitrogen gas was dried by passage through P2O5. Water was deion-
J = 9.1 Hz, 2 H), 6.30 (d, J = 15.8 Hz, 1 H), 5.95 (td, J = 7.3, 15.8
Hz 1 H), 3.56 (d, J = 7.3 Hz, 2 H), 3.80 (s, 3 H).
Synthesis 2008, No. 12, 1960–1964 © Thieme Stuttgart · New York

SPECIAL TOPIC
Palladium-Catalyzed p-Allylic Sulfonylation in Water
MS (EI): m/z (%) = 237 (3, M+ + H), 143 (99), 95 (bp).
1963
13C NMR (CDCl3): d = 159.8, 138.6, 133.6, 130.9, 129.0, 128.5,
127.8, 127.6, 114.0, 112.5, 60.5, 55.2.
cis-5-Methoxycarbonylcyclohex-2-enyl Phenyl Sulfone (5)
MS (EI): m/z (%) = 288 (10, M+), 197 (9), 115 (bp), 51 (67).
IR (ATR): 2979, 1731, 1085 cm–1.
3-(Phenylsulfonyl)-1,3-diphenylprop-2-ene (3e)
1H NMR (CDCl3): d = 7.87 (d, J = 7.8 Hz, 2 H), 7.67 (t, J = 7.8 Hz,
1 H), 7.57 (t, J = 7.8 Hz, 2 H), 6.05–6.02 (m, 1 H), 5.90 (d, J = 10.2
Hz, 1 H), 3.92–3.89 (m, 1 H), 3.69 (s, 3 H), 2.57–2.53 (m, 1 H),
2.40–2.38 (m, 1 H), 2.33–2.25 (m, 1 H), 2.10–2.02 (m, 1 H), 5.67
(d, J = 10.3 Hz, 1 H), 3.99 (br s, 1 H), 3.72 (s, 3 H), 2.67 (dddd,
J = 12.2, 9.7, 6.4, 2.4 Hz, 1 H), 2.42–2.24 (m, 3 H), 1.72 (ddd,
J = 12.3, 12.3, 12.3 Hz, 1 H).
13C NMR (CDCl3): d = 174.1, 136.3, 133.8, 132.5, 129.1, 129.0,
118.9, 62.7, 52.1, 38.1, 27.2, 25.5.
MS (EI): m/z (%) = 280 (0.3, M+), 139 (16), 79 (bp), 51 (30).
IR (ATR): 3060, 1142, 1082 cm–1.
1H NMR (CDCl3): d = 7.65 (d, J = 7.3 Hz, 2 H), 7.54 (t, J = 7.3 Hz,
1 H), 7.39 (t, J = 7.3 Hz, 2 H), 7.35–7.25 (m, 10 H), 6.56 (dd,
J = 15.6, 8.7 Hz, 1 H), 6.49 (d, J = 15.6 Hz, 1 H), 4.81 (d, J = 8.7
Hz, 1 H).
13C NMR (CDCl3): d = 156.4, 155.6, 154.1, 150.5, 148.0, 147.6,
147.2, 147.0, 146.9, 146.9, 146.8, 145.0, 138.2, 93.7.
MS (EI): m/z (%) = 334 (0.5, M+), 191 (42), 115 (bp), 91 (41).
Geranyl Phenyl Sulfone (3f)
Palladium-Catalyzed Asymmetric Allylic Substitution of Cy-
clic Allyl Esters with Sodium Benzenesulfinate; (S)-3-(Phenyl-
sulfonyl)cyclohept-1-ene [(S)-3k]; Typical Procedure
IR (ATR): 2918, 1446, 1294, 1144, 1085 cm–1.
1H NMR (CDCl3): d = 7.88–7.85 (m, 2 H), 7.65–7.61 (m, 1 H),
7.55–7.51 (m, 2 H), 5.18 (t, J = 8.0 Hz, 1 H), 5.02 (m, 1 H), 3.80 (d,
J = 8.0 Hz, 2 H), 2.18–1.94 (m, 4 H), 1.68 (s, 3 H), 1.58 (s, 3 H),
1.31 (s, 3 H).
13C NMR (CDCl3): d = 146.3, 138.6, 133.4, 132.0, 128.9, 128.5,
123.4, 110.2, 56.0, 39.6, 26.1, 25.6, 17.6, 16.1.
To a mixture of the catalyst 6 (89 mg, 0.025 mmol) and methyl cy-
cloheptenyl carbonate (2k; 85.0 mg, 0.5 mmol) in H2O (2.0 mL)
was added sodium benzenesulfinate (150 mg, 0.75 mmol) and the
mixture was stirred at 25 °C for 1 h. The mixture was filtered and
the recovered resin beads were rinsed with EtOAc (3 mL). The
EtOAc layer was separated and the aqueous layer was extracted
with EtOAc (5 mL). The combined EtOAc extracts were washed
with brine (2 mL) and dried (MgSO4). The solvent was evaporated
and the residue was chromatographed on silica gel (hexane–
MS (EI): m/z (%) = 169 (1, M+ – O2Ph), 141 (10), 77 (91), 41 (bp).
Linalyl Phenyl Sulfone (3h)
IR (ATR): 2918, 1446, 1294, 1144, 1085 cm–1.
19
EtOAc, 2:1) to give 65 mg (84%) of (S)-3k; [a]D –145 (c 1.0,
1H NMR (CDCl3): d = 7.77 (d, J = 8.3 Hz, 2 H), 7.59 (d, J = 8.3 Hz,
1 H), 7.48 (t, J = 8.3 Hz, 2 H), 5.89 (dd, J = 17.5, 10.7 Hz, 1 H), 5.33
(d, J = 10.7 Hz, 1 H), 5.03 (d, J = 17.5 Hz, 1 H), 5.01 (m, 1 H),
1.96–1.83 (m, 4 H), 1.63 (s, 3 H), 1.52 (s, 3 H), 1.34 (s, 3 H).
13C NMR (CDCl3): d = 135.1, 133.4, 130.7, 128.8, 128.2, 123.0,
120.4, 110.2, 68.2, 32.7, 25.5, 22.4, 17.6, 16.1.
CH2Cl2); ee 71% {Lit.15 [a]D25 –89.6 (c 3.84, CH2Cl2) for (S)-3k of
94% ee}. The enantiomeric excess was determined by HPLC anal-
ysis using a chiral stationary phase column [Chiralcel OD-H (500
mm); eluent: n-hexane–i-PrOH, 9:1; flow rate: 0.5 mL/min; tR:
major isomer 59 min and minor isomer 62 min].
Spectral data of (S)-3k were identical with that of 3k given above.
MS (EI): m/z (%) = 169 (1, M+ – O2Ph), 141 (10), 77 (91), 41 (bp).
(S)-3i
[a]D20 –179.9 (c 0.45, CH2Cl2); ee 45% {Lit.15 [a]D20 –216.6 (c 1.56,
CH2Cl2) for (S)-3i of 98% ee}. The enantiomeric excess was deter-
mined by HPLC analysis using a chiral stationary phase column
[Chiralcel OD-H (500 mm); eluent: n-hexane–i-PrOH, 9:1; flow
rate: 0.5 mL/min; tR: major isomer 77 min and minor isomer 82
min].
3-(Phenylsulfonyl)cyclopent-1-ene (3i)
IR (ATR): 2936, 1302, 1138, 1084 cm–1.
1H NMR (CDCl3): d = 7.88 (d, J = 7.3 Hz, 2 H), 7.65 (t, J = 7.3 Hz,
1 H), 7.54 (t, J = 7.3 Hz, 2 H), 6.12–6.10 (m, 1 H), 5.68–5.66 (m, 1
H), 4.29–4.27 (m, 1 H), 2.39–2.13 (m, 4 H).
13C NMR (CDCl3): d = 140.2, 137.5, 133.5, 129.0, 128.8, 123.7,
72.3, 31.8, 24.4.
Spectral data of (S)-3i were identical with that of 3i given above.
MS (EI): m/z (%) = 209 (0.1, M+ + H), 143 (6), 67 (bp).
(S)-3j
20
20
[a]D –60.0 (c 0.4, CH2Cl2); ee 33% {Lit.15 [a]D –136.8 (c 3.84,
CH2Cl2) for (S)-3j of 98% ee}. The enantiomeric excess was deter-
mined by HPLC analysis using a chiral stationary phase column
[Chiralcel AD-H (500 mm); eluent: n-hexane–i-PrOH, 9:1; flow
rate: 0.5 mL/min; tR: major isomer 68 min and minor isomer 71
min].
3-(Phenylsulfonyl)cyclohex-1-ene (3j)
IR (ATR): 2938, 1302, 1084 cm–1.
1H NMR (CDCl3): d = 7.88 (d, J = 7.8 Hz, 2 H), 7.65 (t, J = 7.8 Hz,
1 H), 7.55 (t, J = 7.8 Hz, 2 H), 6.10–6.07 (m, 1 H), 5.79–5.77 (m, 1
H), 3.77–3.75 (m, 1 H), 2.01–1.73 (m, 5 H), 1.53–1.46 (m, 1 H).
13C NMR (CDCl3): d = 137.3, 135.2, 133.5, 129.1, 128.9, 118.4,
61.7, 24.3, 22.6, 19.4.
Spectral data of (S)-3j were identical with that of 3j given above.
MS (EI): m/z (%) = 223 (33, M+ + H), 143 (99), 77 (bp).
Acknowledgment
This work was supported by the CREST program, sponsored by the
JST. We also thank the MEXT (Scientific Research on Priority
Areas, No. 460) for partial financial support of this work.
3-(Phenylsulfonyl)cyclohept-1-ene (3k)
IR (ATR): 2926, 1303, 1084 cm–1.
1H NMR (CDCl3): d = 7.91 (d, J = 8.2 Hz, 2 H), 7.65 (t, J = 8.2 Hz,
1 H), 7.56 (t, J = 8.2 Hz, 2 H), 6.04–5.99 (m, 1 H), 5.82–5.79 (m, 1
H), 3.86–3.83 (m, 1 H), 2.23–2.19 (m, 2 H), 2.08–2.20 (m, 2 H),
1.72–1.58 (m, 3 H), 1.46–1.44 (m, 1 H).
13C NMR (CDCl3): d = 137.8, 136.8, 133.5, 129.0, 128.9, 123.7,
66.2, 27.9, 27.8, 26.8, 25.9.
References
(1) For reviews, see: (a) Fuchs, P. L.; Braish, T. F. Chem. Rev.
1986, 86, 903. (b) Roberts, D. W.; Williams, D. L.
Tetrahedron 1987, 43, 1027.
Synthesis 2008, No. 12, 1960–1964 © Thieme Stuttgart · New York

1964
Y. Uozumi, T. Suzuka
SPECIAL TOPIC
(9) For reviews on heterogeneous-switching of organic
(2) (a) Trost, B. M.; Ghadiri, M. R. J. Am. Chem. Soc. 1984, 106,
7260. (b) Trost, B. M.; Schmuff, N. R.; Miller, M. J. J. Am.
Chem. Soc. 1980, 102, 5979. (c) Chandrasekhar, S.; Yu, J.;
Falck, J. R. Tetrahedron Lett. 1994, 35, 5441. (d) Smith, T.
A. K.; Whithan, G. H. J. Chem. Soc., Perkin Trans. 1 1989,
313. (e) Padwa, A.; Bullock, W. H.; Dyszlewski, A. D.
J. Org. Chem. 1990, 55, 955. (f) Ponten, F.; Magnusson, G.
J. Org. Chem. 1996, 61, 7463. (g) Julia, M.; Nel, M.;
Saussine, L. J. Organomet. Chem. 1979, 181, C17.
(3) (a) Inomata, K.; Yamamoto, T.; Kotake, H. Chem. Lett.
1981, 1357. (b) Trost, B. M.; Schmuff, N. R. J. Am. Chem.
Soc. 1985, 107, 396.
transformations, see: (a) Bailey, D. C.; Langer, S. H. Chem.
Rev. 1981, 81, 109. (b) Shuttleworth, S. J.; Allin, S. M.;
Sharma, P. K. Synthesis 1997, 1217. (c) Shuttleworth, S. J.;
Allin, S. M.; Wilson, R. D.; Nasturica, D. Synthesis 2000,
1035. (d) Dörwald, F. Z. Organic Synthesis on Solid Phase;
Wiley-VCH: Weinheim, 2000. (e) Leadbeater, N. E.;
Marco, M. Chem. Rev. 2002, 102, 3217. (f) Ley, S. V.;
Baxendale, I. R.; Bream, R. N.; Jackson, P. S.; Leach, A. G.;
Longbottom, D. A.; Nesi, M.; Scott, J. S.; Storer, R. I.;
Taylor, S. J. J. Chem. Soc., Perkin Trans. 1 2000, 3815.
(g) McNamara, C. A.; Dixon, M. J.; Bradley, M. Chem. Rev.
2002, 102, 3275. (h) Chiral Catalyst Immobilization and
Recycling; De Vos, D. E.; Vankelecom, I. F. J.; Jacobs, P.
A., Eds.; Wiley-VCH: Weinheim, 2000.
(4) Felpin, F.-X.; Landais, Y. J. Org. Chem. 2005, 70, 6441.
(5) Liano, M.-C.; Duan, X.-H.; Liang, Y.-M. Tetrahedron Lett.
2005, 46, 3469.
(6) For studies on polymer-supported catalysts from the senior
author’s group, see: (a) Cross-coupling: Uozumi, Y.; Danjo,
H.; Hayashi, T. J. Org. Chem. 1999, 64, 3384.
(10) For a recent review of solid-phase reactions using palladium
catalysts, see: (a) Uozumi, Y.; Hayashi, T. Solid-Phase
Palladium Catalysis for High-Throughput Organic
Synthesis, In Handbook of Combinatorial Chemistry;
Nicolaou, K. C.; Hanko, R.; Hartwig, W., Eds.; Wiley-VCH:
Weinheim, 2002, Chap. 19. (b) Uozumi, Y. Top. Curr.
Chem. 2004, 242, 77.
(b) Carbonylation reaction: Uozumi, Y.; Watanabe, T.
J. Org. Chem. 1999, 64, 6921. (c) Michael addition:
Shibatomi, K.; Nakahashi, T.; Uozumi, Y. Synlett 2000,
1643. (d) Suzuki–Miyaura coupling: Uozumi, Y.; Nakai, Y.
Org. Lett. 2002, 4, 2997. (e) Heck reaction: Uozumi, Y.;
Kimura, T. Synlett 2002, 2045. (f) Rhodium catalysis:
Uozumi, Y.; Nakazono, M. Adv. Synth. Catal. 2002, 344,
274. (g) Wacker cyclization: Hocke, H.; Uozumi, Y. Synlett
2002, 2049. (h) Wacker cyclization: Hocke, H.; Uozumi, Y.
Tetrahedron 2003, 59, 619. (i) Sonogashira reaction:
Uozumi, Y.; Kobayashi, Y. Heterocycles 2003, 59, 71.
(j) Oxidation: Uozumi, Y.; Nakao, R. Angew. Chem. Int. Ed.
2003, 42, 194. (k) Oxidation: Uozumi, Y.; Nakao, R.
Angew. Chem. Int. Ed. 2003, 42, 194. (l) Suzuki–Miyaura
coupling: Uozumi, Y.; Kikuchi, M. Synlett 2005, 1775.
(m) Reduction: Nakao, R.; Rhee, H.; Uozumi, Y. Org. Lett.
2005, 7, 163. (n) Alkylation: Yamada, Y. M. A.; Uozumi, Y.
Org. Lett. 2006, 8, 1375. (o) Oxidation: Yamada, Y. M. A.;
Arakawa, T.; Hocke, H.; Uozumi, Y. Angew. Chem. Int. Ed.
2007, 46, 704.
(11) One preliminary example (Table 1, entry 5) has been
reported in reference 7b.
(12) For studies on heterogeneous aquacatalytic asymmetric p-
allylic transformations with polymer-supported complex
catalysts in water, see: (a) Alkylation: Uozumi, Y.; Danjo,
H.; Hayashi, T. Tetrahedron Lett. 1998, 39, 8303.
(b) Reduction with MOP: Hocke, H.; Uozumi, Y.
Tetrahedron 2004, 60, 9297. (c) Alkylation: Uozumi, Y.;
Shibatomi, K. J. Am. Chem. Soc. 2001, 123, 2919.
(d) Amination: Uozumi, Y.; Tanaka, H.; Shibatomi, K. Org.
Lett. 2004, 6, 281. (e) Cyclization: Nakai, Y.; Uozumi, Y.
Org. Lett. 2005, 7, 291. (f) Etherification: Uozumi, Y.;
Kimura, M. Tetrahedron: Asymmetry 2006, 17, 161.
(g) Nitromethylation: Uozumi, Y.; Suzuka, T. J. Org. Chem.
2006, 71, 8644.
(13) Purchased from Rapp Polymere GmbH, Tübingen,
Germany.
(7) For studies on p-allylic transformations with polymer-
supported complex catalysts in water, see: (a) Uozumi, Y.;
Danjo, H.; Hayashi, T. Tetrahedron Lett. 1997, 38, 3557.
(b) Danjo, H.; Tanaka, D.; Hayashi, T.; Uozumi, Y.
Tetrahedron 1999, 55, 14341. (c) Uozumi, Y.; Suzuka, T.;
Kawade, R.; Takenaka, H. Synlett 2006, 2109.
(14) For a recent review on asymmetric p-allylic substitution,
see: (a) Acemoglu, L.; Williams, J. M. J. Handbook of
Organopalladium Chemistry; Negishi, E., Ed.; Wiley: New
York, 2002. (b) Trost, B. M.; Crawley, M. L. Chem. Rev.
2003, 103, 2921.
(8) For reviews on aqueous-switching of organic
transformations, see: (a) Li, C.-J.; Chan, T.-H. Organic
Reactions in Aqueous Media; Wiley-VCH: Weinheim,
1997. (b) Grieco, P. A. Organic Synthesis in Water; Kluwer
Academic Publishers: Dordrecht, 1997. (c) Herrmann, W.
A.; Kohlpaintner, C. W. Angew. Chem., Int. Ed. Engl. 1993,
32, 1524. (d) Lindström, U. M. Chem. Rev. 2002, 102, 2751.
(15) (a) Trost, B. M.; Organ, M. G.; O’Doherty, G. A. J. Am.
Chem. Soc. 1995, 117, 9662; and references cited therein.
(b) Trost, B. M.; Radinov, R. J. Am. Chem. Soc. 1997, 119,
5962.
(16) (a) Trost, B. M.; Merlic, C. A. J. Org. Chem. 1990, 55,
1127. (b) Trost, B. M.; Merlic, C. A. J. Am. Chem. Soc.
1990, 112, 9590.
Synthesis 2008, No. 12, 1960–1964 © Thieme Stuttgart · New York