Palladium-catalyzed asymmetric hydrovinylation under mild conditions using monodentate chiral spiro phosphoramidite and phosphite ligands

Article abstract of DOI:10.1016/j.tetasy.2004.12.017

Palladium complexes of chiral spiro phosphoramidite and phosphite ligands are effective catalysts in the asymmetric hydrovinylation of vinylarenes with ethylene. The hydrovinylation products were obtained in modest selectivity with enantioselectivities up to 92% ee. The structures of the palladium catalysts have been analyzed by X-ray diffraction. The active catalyst contained one monodentate ligand. A kinetic resolution accompanied the isomerization of the hydrovinylation product in the reaction.

Full text of DOI:10.1016/j.tetasy.2004.12.017

Tetrahedron:
Asymmetry
Tetrahedron: Asymmetry 16 (2005) 705–710
Palladium-catalyzed asymmetric hydrovinylation under
mild conditions using monodentate chiral spiro phosphoramidite
and phosphite ligands
Wen-Jian Shi, Jian-Hua Xie and Qi-Lin Zhou*
State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
Received 16 November 2004; accepted 21 December 2004
Available online 26 January 2005
Abstract—Palladium complexes of chiral spiro phosphoramidite and phosphite ligands are effective catalysts in the asymmetric
hydrovinylation of vinylarenes with ethylene. The hydrovinylation products were obtained in modest selectivity with enantioselec-
tivities up to 92% ee. The structures of the palladium catalysts have been analyzed by X-ray diffraction. The active catalyst contained
one monodentate ligand. A kinetic resolution accompanied the isomerization of the hydrovinylation product in the reaction.
ꢀ
2005 Elsevier Ltd. All rights reserved.
1
. Introduction
and provided 3-aryl-1-butene in high enantioselectivity
by choosing a suitable chiral ligand. Recently, we have
developed a new type of monodentate phosphoramidite
The catalytic asymmetric hydrovinylation of olefins is an
important stereoselective carbon–carbon bond forming
reaction in organic synthesis. In particular the asym-
metric hydrovinylation of vinylarenes can afford chiral
0
and phosphite ligands containing a 1,1 -spirobiindane
backbone and demonstrated they were highly efficient
for the rhodium-catalyzed asymmetric hydrogenation
1
5
3
-aryl-1-butenes, which are starting materials for the
of functionalized olefins, copper-catalyzed 1,4-addition
6
7
synthesis of 2-arylpropionic acids, anti-inflammatory
drugs, such as Ibuprofen and Naproxen. Recently, the
nickel-catalyzed hydrovinylation of olefins has been
intensively studied and high regioselectivity and excel-
lent enantioselectivity (up to 95% ee) have been
of dialkylzincs to enones, and other reactions. Herein,
we describe the application of these highly rigid spiro
phosphoramidite and phosphite ligands in the palla-
dium-catalyzed
vinylarenes.
asymmetric
hydrovinylation
of
2
achieved. However, much less attention has been paid
to palladium-catalyzed asymmetric hydrovinylation,
due to the concomitant isomerization of the hydrovinyl-
ation product 3-aryl-1-butene to achiral 2-aryl-2-bu-
tenes. Salzer reported a remarkable enantioselectivity
2
. Results and discussion
Chiral ligands are crucial for the palladium-catalyzed
asymmetric hydrovinylation of vinylarenes with ethyl-
ene. Besides the enantioselectivity of the primary prod-
ucts 3-aryl-1-butenes, the regioselectivity and the
isomerization of the 3-aryl-1-butene to 2-aryl-2-butene
also vary according to the ligand used. To search for effi-
cient chiral ligands in Pd-catalyzed asymmetric hydro-
vinylation, we investigated various monodentate
phosphorus ligands including those with a hemilabile
coordinating group. Preliminary experiments showed
that spiro phosphoramidite and phosphite ligands
(
vinylation of styrene using a chiral phosphine ligand
92% ee) in the palladium-catalyzed asymmetric hydro-
6
derived from tricarbonyl(g -ethylbenzene)chromium,
but the yield of the desired product 3-phenyl-1-butene
3
was not high. Employing P-stereogenic ligands, such
as benzylmesitylphenylphosphine, Granell et al.
obtained the hydrovinylation product in excellent yield
and good enantioselectivity (84% ee) in the reaction of
4
2
-vinylnaphthalene. These results indicated that palla-
dium-catalyzed asymmetric hydrovinylation could sur-
mount the concomitant isomerization of the products
(
Fig. 1) are effective.
*
Corresponding author. Tel.: +86 22 23500011; fax: +86 22
3506177; e-mail: qlzhou@nankai.edu.cn
The hydrovinylation reaction took place in dichlorome-
thane at 25 ꢁC under 10 bar of ethylene in the presence
2
0
957-4166/$ - see front matter ꢀ 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2004.12.017

706
W.-J. Shi et al. / Tetrahedron: Asymmetry 16 (2005) 705–710
R
R N
Ph
N
N
Ph
P
P
P
O
O
O
O
O
O
a R = Me
b R = i-Pr
c R = -(CH ) -
2
4
(
(
R,R,R)-2
R,S,S)-2
(R,R)-3
(R,S)-3
(
R)-1
OMe
O
Ar
O
N
P
P
P
OMe
O
O
O
O
O
O
a Ar = Ph
b Ar = 2,6-Me Ph
2
(
(
R,R)-4
R,S)-4
(R,R)-6
(R,S)-6
(
R)-5
Figure 1. Spiro phosphoramidite and phosphite ligands.
of 0.5 mol% of palladium catalyst prepared in situ from
[
From the data in Table 1, some conclusions can be
drawn: (1) The phosphoramidite ligands bearing larger
alkyl groups on the nitrogen atom gave higher conver-
sion of styrene and higher enantioselectivity of the
hydrovinylation product 7. (2) Introducing a chiral
amino moiety into the phosphoramidite ligand did not
give a positive influence on the selectivity of reaction.
(3) Adding a hemilabile methoxy group to the ligands
did not significantly improve the reaction.
3
Pd(g -C H )(COD)]BF and the ligand (0.5 mol%).
3 5 4
After stirring for several hours, the reaction was
quenched with aqueous ammonium chloride, and the
products were purified by chromatography on a short
silica gel column and analyzed by GC. It was found that
the hydrovinylation reaction was accompanied by the
isomerization of product 7. Prolonging the reaction time
increased the conversion of styrene, but the amount of
isomerization product 8 increased simultaneously. Table
1 summarizes the best results obtained with spiro
monodentate ligands 1–6.
Using (R)-1b as a standard ligand, we further studied the
influence of counter anions, which play an important
a
Table 1. Pd-catalyzed asymmetric hydrovinylation, ligand comparison
*
[
Pd(allyl)(COD)]BF / L
4
+
+
Oligomers
+
o
CH Cl , 10 bar, 25 C
2
2
7
8
b
c
d
Entry
Ligand
Time (h)
Conv (%)
Selectivity (%)
Ee of 7 (%)
7
8
Oligomers
1
2
3
4
5
6
7
8
9
(R)-1a
(R)-1b
(R)-1c
7
7
11
86
88
51
83
80
61
69
69
—
79
64
69
44
26
9
48
4
3
1
17 (S)
38 (S)
18 (S)
24 (S)
23 (S)
26 (S)
9 (S)
12
7
6
10
13
16
1
(R,R,R)-2
(R,S,S)-2
(R,R)-3
(R,S)-3
(R,R)-4
(R,S)-4
(R)-5a
4
3
80
42
38
25
27
—
15
30
25
55
73
12
12
12
12
13
1
6
33
4
Trace
28
47
—
6
—
20 (S)
34 (S)
33 (S)
21 (S)
36 (S)
10
11
12
13
6
(R)-5b
(R,S)-6
(R,R)-6
61
70
6
8
1
5
85
1
a
b
c
3
Reaction conditions: Styrene/Pd/L = 200:1:1, 3 mL CH
Determined by GC using a HP-5 column.
Based on the converted styrene.
2
Cl
2
, [Pd(g -C
3
5 4
H )(COD)]BF as catalyst precursor.
d
Determined by chiral GC using a Suplco b-DEX 120 column.

W.-J. Shi et al. / Tetrahedron: Asymmetry 16 (2005) 705–710
707
a
Table 2. The counter anion effect in Pd-catalyzed hydrovinylation of styrene
Entry
Ligand
Anion
Time (h)
Conv (%)
Selectivity (%)
Ee of 7 (%)
7
8
Oligomers
ꢀ
4ꢀ
1
2
3
(R)-1b
(R)-1b
(R)-1b
(R)-1b
(R)-1b
OTf
BF
5.0
7.0
5.0
7.0
1.5
31
86
56
63
48
65
51
77
66
76
9
48
17
19
14
3
26
1
27 (S)
38 (S)
40 (S)
47 (S)
58 (S)
6ꢀ
6ꢀ
PF
SbF
6
b
4
15
10
ꢀ
5
BARF
a
2 2 3 5 2
Reaction conditions: Styrene/Pd/1b = 200:1:1, 10 bar (initial pressure) ethylene, 25 ꢁC, 3 mL CH Cl , [Pd(g -C H )Cl] as catalyst precursor; AgX
ꢀ
+
or NaBARF ([3,5-(CF ) C H ] B [Na] ) as coactivator.
3 2 6 3 4
b
At 0 ꢁC.
role in various olefin dimerization and related reac-
8
but the reaction became very slow (entry 8). The hydro-
vinylation reaction can also be performed with a lower
catalyst loading (S/C = 600), providing a similar result
(entry 9).
tions. The results are summarized in Table 2. Consis-
tent with the Ni-catalyzed asymmetric hydrovinylation
2
b
2c
reported by RajanBabu and Leinter and co-workers,
a counter anion effect was observed in palladium-cata-
lyzed hydrovinylation. The catalyst with the weakly
coordinating anion TfO gave a poorer result in terms
Under the optimized conditions, various vinylarenes
were investigated in the hydrovinylation reaction. As
shown in Table 4, the reactions for all vinylarene sub-
strates were fast, finishing in 2 h. An electronic effect
of substituents on the phenyl ring of styrene was ob-
served. The styrenes substituted with electron-withdraw-
ing groups, such as Cl or Br, gave poor enantio-
selectivities (entries 2 and 3), whereas those with
electron-donating groups, such as methyl and iso-butyl,
provided higher enantioselectivities (entries 4–6). The
highest enantioselectivity was achieved in the hydrovinyl-
ation of 4-methylstyrene.
ꢀ
of both reactivity and enantioselectivity (Table 2, entry
). Using a bulkier and more dissociating anions, such
1
ꢀ
ꢀ
ꢀ
as BF4 , PF6 , and SbF6 significantly improved the
reactivity and the enantioselectivity of the reaction
(entries 2–4). The highest enantioselectivity (58% ee)
was achieved by using the catalyst with BARF anion.
ꢀ
Further optimization of the reaction conditions for
asymmetric hydrovinylation of styrene was performed
employing ligand 1b and coactivitor NaBARF. Solvent
screening showed that the reaction was very sensitive
to the solvent used. In coordinating solvents, such as
THF, no reaction occurred (Table 3, entry 6). However,
higher reactivity and enantioselectivity were obtained in
weakly coordinating nonpolar solvents, such as toluene
and chlorobenzene (entries 2 and 3). As for protic sol-
vents, for example, methanol, even a small amount com-
pletely quenched the reaction. The hydrovinylation
under 1 bar of ethylene gave almost the same results
as the reaction under 10 bar of ethylene, implying that
the pressure of ethylene is not a controlling factor to
the reaction (entry 7). When the reaction was carried
out at 0 ꢁC, the enantioselectivity increased to 68% ee,
The catalytic hydrovinylation of vinylarenes is concomi-
tant with the isomerization of the product 3-aryl-1-bu-
tene to the achiral 2-aryl-2-butene, which increased with
prolonging reaction time. In the hydrovinylation of 4-
methylstyrene, we found that when the reaction was
quenched in 60 min, the conversion was 65%, and the
selectivity of 3-(4-methylphenyl)-1-butene was 71% in
68% ee (entry 4). When the reaction time was prolonged
to 120 min, the substrate 4-methylstyrene was com-
pletely converted, and the selectivity of 3-(4-methylphen-
yl)-1-butene dramatically dropped to 10%, while the
enantioselectivity increased to 92% ee (entry 6). These
a
Table 3. Solvent, pressure, and temperature effect in the hydrovinylation of styrene
Entry
Solvent
Time (h)
Conv (%)
Selectivity (%)
Ee of 7 (%)
7
8
Oligomers
1
2
3
4
5
6
CH Cl
Toluene
PhCl
2
2
1.5
0.5
48
85
62
38
20
76
58
76
78
86
—
57
63
49
14
30
16
13
4
10
12
8
58 (S)
63 (S)
62 (S)
26 (S)
60 (S)
—
0.5
CH
Et
3
NO
2
15.0
15.0
15.0
1.0
10
10
—
11
13
28
2
O
b
THF
N.R.
—
32
24
23
c
7
Toluene
Toluene
Toluene
88
83
86
64 (S)
68 (S)
63 (S)
c,d
8
e
12.0
1.5
9
a
3
3 5 2
Reaction conditions: Styrene/[Pd]/1b = 200:1:1, 10 bar ethylene, 25 ꢁC, 3 mL solvent, [Pd(g -C H )Cl] as catalyst precursor, NaBARF as coac-
tivator unless otherwise stated.
No reaction.
b
c
Under 1 bar ethylene.
At 0 ꢁC.
S/C = 600.
d
e

708
W.-J. Shi et al. / Tetrahedron: Asymmetry 16 (2005) 705–710
a
Table 4. Palladium-catalyzed asymmetric hydrovinylation of vinylarenes and ethylene
0
.5 mol%[Pd (C H )Cl]/(R)-1b
3 5
Ar
+
Ar
+ Ar
+ Oligomers
o
NaBARF, Toluene, 1 bar, 25 C
9
10
b
c
Entry
Substrate
Styrene
Time (min)
Conv (%)
Selectivity (%)
Ee of 9 (%)
9
10
Oligomers
1
2
3
4
5
6
7
8
9
60
15
88
56
57
78
62
71
41
10
72
72
85
32
18
32
11
45
75
15
25
15
11
4
64 (S)
20
36
4-Bromostyrene
3-Chlorostyrene
4-Methylstyrene
4-Methylstyrene
4-Methylstyrene
3-Methystyene
45
60
72
65
6
18
14
15
13
3
68
77
100
120
30
98
100
75
92
72
4-i-Bu-styrene
2-Vinylnaphthanlene
45
120
79
73
76
55 (S)
d
0
a
3
Reaction conditions: vinylarene/Pd/1b = 200:1:1, 1 bar ethylene, 25 ꢁC, 3 mL toluene, [Pd(g -C
coactivator.
3 5 2
H )Cl] as catalyst precursor, NaBARF as
b
c
Determined by GC using a HP-5 column.
Determined by chiral GC using a Suplco b-DEX 120 column.
Determined by chiral HPLC using a Chiralcel OJ column.
d
3
3
Figure 2. Crystal structures of [Pd(g -C
3
H
5
)((R)-1b)2]BF
4
(a) and [Pd(g -C
3
H
5
)Cl((R)-5a)] (b), anions are omitted for clarity.
results indicated that a kinetic resolution accompanied
3
isomerization of the hydrovinylation product.
3. Conclusion
In summary, we have established a new efficient catalytic
system for palladium-catalyzed asymmetric hydrovinyl-
ation of vinylarenes using monodentate chiral spiro
phosphoramidite and phosphite ligands. Moderate to
good chemoselectivity and enantioselectivity have been
achieved in the reaction. The isomerization of hydro-
vinylation products 3-aryl-1-butene to the achiral 2-
aryl-2-butene was accompanied by a kinetic resolution,
which is beneficial to the increase of enantiomerical pur-
ity of hydrovinylation product. X-ray analysis of crystal
structures revealed that the active catalyst contained one
monodentate ligand.
To understand the structure of catalyst and the features
of the reaction, we grew two single crystals of palladium
3
complex of [Pd(g -C H )Cl] with ligands 1b and 5a,
3
5
2
which are suitable for X-ray diffraction analysis (Fig.
9
3
2
has a C -symmetric structure with two phosphoramidite
). The complex [Pd(g -C H )((R)-1b) ]BF (Fig. 2, a)
3 5 2 4
2
ligands coordinated to palladium in a square planar
10
3
geometry. The complex [Pd(g -C H )Cl((R)-5a)]
3
5
(
Fig. 2, b) has a tetrahedron geometry with one ligand
3
coordinated to palladium. When the crystal of [Pd(g -
C H )Cl((R)-5a)] was used as catalyst, the hydrovinyla-
3
5
tion of styrene proceeded smoothly, and the results are
the same as those with the in situ prepared catalyst.
3
But using the crystal of [Pd(g -C H )((R)-1b) ]BF ,
4. Experimental
4.1. General
3
5
2
4
which has two ligands coordinated, as a catalyst gave
no reaction. These experimental results demonstrated
that more than one monodentate ligands coordinated
to palladium strongly inhibit the hydrovinylation reac-
tion. This might be due to the lack of coordinating site
on palladium for a second olefin coming into the puta-
All reactions and manipulations were performed in
a nitrogen atmosphere using standard Schlenk techni-
1
13
31
ques. H, C, and P NMR spectra were recorded on
Brucker-300 spectrometers. Chemical shifts were
1
1
tive benzylic metal intermediate.

W.-J. Shi et al. / Tetrahedron: Asymmetry 16 (2005) 705–710
709
reported in ppm downfield from internal Si(CH ) and
3
121.2, 120.8, 120.6, 118.6, 113.9, 38.4, 37.8, 30.8, 30.4.
HR-MS (FAB) calcd for C H O P + H: 581.1876.
Found: 581.1866.
4
external 85% H PO , respectively. Optical rotations
3
4
38 29
4
were determined using a Perkin Elmer 341 polarimeter.
HR-MS were recorded on APEXII and ZAB-HS spec-
trometer. Melting points were measured on a RY-I
apparatus and uncorrected. GC analyses were per-
formed using Hewlett Packard Model HP 6890 Series.
Toluene and THF were distilled from sodium-benzophe-
none ketyl under nitrogen. Methylene chloride, chloro-
benzene, and nitromethane were distilled from CaH2
under nitrogen atmosphere. Styrene was distilled from
0
0
0
4.2.3. (R)-[2-(2 -Methoxy-1,1 -binaphthyl)]-[(R)-1,1 -spi-
robiindane-7,7 -diyl]phosphite (R,R)-6. Ligand (R,R)-6
0
0
was synthesized in 70% yield with (R)-2 -methoxyl-
0
1
,1 -binaphthyl-2-ol using the same procedure as that
25
D
for (R)-5b. Mp: 210–212 ꢁC. ½aꢁ = +68 (c 0.5, CH Cl ).
2
2
1
H NMR (300 MHz, CDCl ): d 8.10–6.17 (m, 18H), 3.79
3
(
(
s, 3H), 3.07–2.87 (m, 2H), 2.80–2.64 (m, 2H), 2.18–2.07
m, 2H), 1.94–1.78 (m, 2H). P NMR (300 MHz,
CaH and stored at low temperature. All vinylarenes
2
31
were purchased from Aldrich except 4-iso-butylstyrene
that was prepared from 4-bromostyrene according to
13
CDCl ): d 119.8. C NMR (300 MHz, CDCl ): d
3
3
155.1, 148.1, 145.9, 144.9, 143.1, 143.0, 139.3, 134.0,
131.0, 130.0, 129.4, 128.3, 128.1, 127.8, 127.1, 126.7,
1
2
the reported literature. The ethylene used had a purity
13
3
14
of >99.99%. [Pd(g -C H )(COD)]BF and NaBARF
3
5
4
1
1
3
5
26.0, 125.7, 124.9, 123.7, 122.3, 121.9, 121.8, 121.3,
21.2, 121.1, 118.5, 113.5, 59.0, 56.4, 38.5, 37.7, 30.9,
0.4. HR-MS (FAB) calcd for C H O P + H:
were prepared according to the literature methods.
Ligands 1, 2, 3, 4 and 5a were prepared by the previ-
7
a
38 29
4
ously reported methods.
81.1876. Found: 581.1875.
4
4
.2. Synthesis of spiro phosphite ligands 5b and 6
4.3. General procedure for the palladium-catalyzed
asymmetric hydrovinylation of vinylarenes
0
0
.2.1.
2,6-Dimethylphenyl-[(R)-1,1 -spirobiindane-7,7 -
diyl]-phosphite (R)-5b. General procedure: To a stirred
solution of PCl3 (110 lL, 1.3 mmol), Et N (380 lL,
2.7 mmol), and THF (25 mL) was added (R)-1,1 -spiro-
0
biindane-7,7 -diol (308 mg, 1.2 mmol) in 5 mL THF at
The mixture of phosphoramidite (R)-1b (3.9 mg,
3
0
3
0.01 mmol) and [Pd(g -C H )Cl] (1.8 mg, 0.005 mmol)
3
5
2
in toluene (2 mL) in a Schlenk tube was stirred at room
temperature for 1 h, and then transferred to another
Schlenk tube which contained a suspension of NaBARF
in toluene (1 mL). The resulted mixture was stirred at
room temperature for 20 min and the color of the solu-
tion turned to yellow. After added styrenes (2.0 mmol),
the oxygen-free ethene (1 atm) was introduced into the
tube. The reaction mixture was vigorously stirred at
25 ꢁC for several hours under the ethene atmosphere
(1 atm). The reaction solution was then diluted with
ꢀ
78 ꢁC and the mixture was stirred for 2 h. After
warming to room temperature, the reaction mixture
was filtered, and the filtrate was cooled to ꢀ78 ꢁC
again. A solution of lithium phenolate prepared from
2
,6-dimethylphenol (166 mg, 1.36 mmol) and n-butyl-
lithium (1.6 M solution in hexane, 0.85 mL, 1.36 mmol)
was added to the above filtrate. After the addition, the
resulting solution was warmed to room temperature,
and was stirred overnight. Then, the reaction mixture
was concentrated in vacuo and the obtained residue
was purified by a flash chromatography on silica gel
using petroleum ether/EtOAc (30:1) as an eluent to give
ether, quenched with a saturated aqueous NH Cl, and
4
washed with brine. The organic layers were separated
and dried over anhydrous Na SO , purified by a short
2
4
(
1
(
(
(
R)-5b as a white solid (367 mg, 76% yield). Mp: 143–
H NMR
silica gel column. The conversion, selectivity, and ee val-
ues of products were analyzed by GC or HPLC.
2
5
1
45 ꢁC. ½aꢁ = +324 (c 0.5, CH Cl ).
D
2
2
300 MHz, CDCl ): d 7.25–6.81 (m, 9H), 3.16–3.04
3
m, 2H), 2.90–2.81 (m, 2H), 2.31–2.26 (m, 2H), 2.24
s, 6H), 2.09–2.0 (m, 2H).
The GC and HPLC conditions for the determinations of
ee values of hydrovinylation products are as follows:
3
1
P NMR (300 MHz,
1
3
CDCl ): d 122.7. C NMR (300 MHz, CDCl ): d
3
3
TM
1
1
1
49.2, 146.2, 145.8, 145.1, 144.1, 144.0, 143.2, 140.2,
30.8, 129.1, 128.6, 127.8, 124.5, 123.0, 122.1, 121.9,
21.8, 121.6, 59.5, 38.9, 38.1, 31.2, 30.7, 18.0. HR-MS
3-Phenyl-1-butene: Supelco b-DEX
120 column,
25 m · 0.25 mm · 0.25 lm; N , 1.2 mL/min; 65 ꢁC (con-
2
stant), t = 37.73 min (R), t = 38.55 min (S).
R
R
(
4
FAB) calcd for C H O P + H: 403.1447. Found:
25 23 3
03.1457.
TM
3-(4-Methylphenyl)-1-butene: Supelco b-DEX
120
column, 25 m · 0.25 mm · 0.25 lm; N , 1.2 mL/min;
2
0
0
0
4.2.2. (S)-[2-(2 -Methoxy-1,1 -binaphthyl)]-[(R)-1,1 -spi-
robiindane-7,7 -diyl]-phosphite (R,S)-6. Ligand (R,S)-6
75 ꢁC (constant), t = 59.18 (minor), t = 60.63 min
R
R
0
(major).
0
was synthesized in 70% yield with (S)-2 -methoxyl-
0
TM
1
,1 -binaphthyl-2-ol using the same procedure as that
3-(4-Bromophenyl)-1-butene: Supelco b-DEX
120
25
for (R)-5b. Mp: 124–125 ꢁC. ½aꢁ = +62 (c 0.5, CH Cl ).
column, 25 m · 0.25 mm · 0.25 lm; N , 1.2 mL/min;
D
2
2
2
1
H NMR (300 MHz, CDCl ): d 8.12–6.67 (m, 18H), 3.70
100 ꢁC for 50 min and then programmed at 1 ꢁC/min
to 120 ꢁC, t = 62.70 (minor), t = 63.58 min (major).
3
(
(
s, 3H), 3.07–2.96 (m, 2H), 2.77–2.70 (m, 2H), 2.20–2.03
m, 2H), 1.93–1.81 (m, 2H). P NMR (300 MHz,
CDCl ): d 118.9. C NMR (300 MHz, CDCl ): d
R
R
3
1
1
3
TM
3-(3-Methylphenyl)-1-butene: Supelco b-DEX
120
3
3
1
1
1
55.6, 148.0, 145.9, 145.1, 143.4, 142.8, 139.5, 134.1,
33.9, 130.8, 130.0, 129.3, 129.2, 128.3, 128.0, 127.3,
26.8, 126.6, 125.9, 125.1, 124.8, 123.8, 122.2, 121.7,
column, 25 m · 0.25 mm · 0.25 lm; N , 1.1 mL/min;
2
80 ꢁC (constant), t = 36.50 (minor), t = 37.32min
R
R
(major).

710
W.-J. Shi et al. / Tetrahedron: Asymmetry 16 (2005) 705–710
TM
3
-(3-Chlorophenyl)-1-butene: Supelco b-DEX
120
Fu, Y.; Xie, J.-H.; Zhou, H.; Wang, L.-X.; Zhou, Q.-L.
Angew. Chem., Int. Ed. 2002, 41, 2348; (c) Fu, Y.; Guo,
X.-X.; Zhu, S.-F.; Hu, A.-G.; Xie, J.-H.; Zhou, Q.-L. J.
Org. Chem. 2004, 69, 4648; (d) Zhu, S.-F.; Fu, Y.; Xie,
J.-H.; Liu, B.; Xing, L.; Zhou, Q.-L. Tetrahedron: Asym-
metry 2003, 14, 3219.
column, 25 m · 0.25 mm · 0.25 lm; N , 1.1 mL/min;
2
7
5 ꢁC for 60 min and then programmed at 1 ꢁC/min to
00 ꢁC, t = 72.75 (minor), t = 73.57 min (major).
1
R
R
TM
3
-(4-Isobutylphenyl)-1-butene: Supelco b-DEX
120
6
. Zhou, H.; Wang, W.-H.; Fu, Y.; Xie, J.-H.; Shi, W.-J.;
Wang, L.-X.; Zhou, Q.-L. J. Org. Chem. 2003, 68,
column, 25 m · 0.25 mm · 0.25 lm; N , 0.3 mL/min;
2
1
1
15 ꢁC for 10 min, programmed at 0.5 ꢁC/min to
30 ꢁC, t = 53.74 (minor), t = 54.25 min (major).
1
582.
R
R
7. (a) Shi, W.-J.; Wang, L.-X.; Fu, Y.; Zhu, S.-F.; Zhou,
Q.-L. Tetrahedron: Asymmetry 2003, 14, 3867; (b) Guo,
X.-X.; Xie, J.-H.; Hou, G.-H.; Shi, W.-J.; Wang, L.-X.;
Zhou, Q.-L. Tetrahedron: Asymmetry 2004, 15, 2231.
. (a) Bayersd o¨ rfer, R.; Ganter, B.; Englert, U.; Keim, W.;
Vogt, D. J. Organomet. Chem. 1998, 552, 187; (b) See
Refs. 2b and c.
3-(2-Naphthalenyl)-1-butene: Chiral Daciel OJ column,
n-hexane as eluent, 0.3 mL/min; t = 56.76 min (R),
tR = 61.03 min (S).
R
8
9
. Crystal data: Orthorhombic, space group P2(1)2(1)2;
˚
a = 20.508(6), b = 24.183(7), c = 10.964(3) [A]; V = 5437(3)
Acknowledgements
˚
3
[
A] , Z = 4, crystal dimensions = 0.2 · 0.20 · 0.12 mm,
We thank the National Natural Science Foundation of
China, the Major Basic Research Development Program
Grant No. G2000077506), the Ministry of Education of
China, and the Committee of Science and Technology of
Tianjin for financial support.
˚
T = 293(2) K, radiation = MoKa, k = 0.71073 [A], unique
data = 9503, R = 0.0424. Crystallographic data (excluding
structure factors) for the structure reported in this paper
have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no CCDC
(
2
59832. Copies of the data can be obtained, free of charge,
on application to CCDC, 12 Union Road, Cambridge
CB2 1EZ: [fax: +44(0) 1223-336033 or deposit@ccdc.cam.
ac.uk].
References and notes
1
0. Crystal data: Orthorhombic, space group P2(1)2(1)2;
˚
a = 7.306(8), b = 14.912(17), c = 21.25(3) [A]; V = 2315(5)
1
. (a) RajanBabu, T. V. Chem. Rev. 2003, 103, 2845; (b)
RajanBabu, T. V. J. Org. Chem. 2003, 68, 8431; (c)
Kumareswaran, R.; Nandi, M.; RajanBabu, T. V. Org.
Lett. 2003, 5, 4345; (d) Zhang, A. B.; RajanBabu, T. V.
Org. Lett. 2004, 6, 1515; (e) Zhang, A.; RajanBabu, T. V.
Org. Lett. 2004, 6, 3159.
˚
3
[A] , Z = 4, crystal dimensions = 0.25 · 0.20 · 0.20 mm,
˚
T = 298(2) K, radiation = MoKa, k = 0.71073 [A], unique
data = 4220, R = 0.0234. Crystallographic data (excluding
structure factors) for the structure reported in this paper
have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no CCDC
259831. Copies of the data can be obtained, free of charge,
on application to CCDC, 12 Union Road, Cambridge
CB2 1EZ: [fax: +44(0) 1223-336033 or deposit@ccdc.
cam.ac.uk].
2
. (a) Wilke, G. Angew. Chem., Int. Ed. Engl. 1988, 27, 185;
(
b) Park, H.; RajanBabu, T. V. J. Am. Chem. Soc. 2002,
24, 734; (c) Franci o´ , G.; Faraone, F.; Leinter, W. J. Am.
Chem. Soc. 2002, 124, 736.
1
3
. Englert, U.; Haerter, R.; Vasen, D.; Salzer, A.; Eggeling,
E. B.; Vogt, D. Organometallics 1999, 18, 4390.
. Albert, J.; Cadena, M.; Granell, J.; Muller, G.; Ordinas, J.
I.; Panyella, D.; Puerta, C.; Sanudo, C.; Valerga, P.
Organometallics 1999, 18, 3511.
11. DiRenzo, G. M. Ph.D. thesis, 1997.
12. Nugent, W. A.; McKinney, R. J. J. Org. Chem. 1985, 50,
5370.
13. Inorg. Synth. 1972, 3, 55.
14. Brookhart, M.; Grant, B.; Volpe, A. Organometallics
1992, 11, 3920.
4
5
. (a) Fu, Y.; Xie, J.-H.; Hu, A.-G.; Zhou, H.; Wang, L.-X.;
Zhou, Q.-L. Chem. Commun. 2002, 480; (b) Hu, A.-G.;