Palladium-catalyzed asymmetric allylic substitutions by axially chiral P,S-, S,S-, and S,O-heterodonor ligands with a binaphthalene framework

Article abstract of DOI:10.1016/j.tetasy.2004.08.008

Axially chiral P,S-heterodonor ligand L1 is quite effective in the asymmetric allylic substitution of 1,3-diphenylpropenyl acetate with dimethyl malonate. Its bidentate coordination pattern to Pd metal center with both P and S atoms has been unambiguously established by X-ray diffraction and NMR spectroscopic analyses. Axially chiral P,S-heterodonor ligand L1 is effective in the asymmetric allylic substitution of 1,3-diphenylpropenyl acetate with dimethyl malonate. Its bidentate coordination pattern to a Pd metal center with both P and S atoms has been unambiguously established by X-ray diffraction and NMR spectroscopic analyses. Herein, we further disclose that axially chiral S,S-heterodonor ligands L2-L4 are also effective in the same reaction to give the allylic alkylation product in moderate to good ee. However, the corresponding S,O-heterodonor ligands are not as effective as the corresponding P,S- or S,S-heterodonor ligands in the same asymmetric reaction.

Full text of DOI:10.1016/j.tetasy.2004.08.008

Tetrahedron:
Asymmetry
Tetrahedron: Asymmetry 15 (2004) 3161–3169
Palladium-catalyzed asymmetric allylic substitutions by axially
chiral P,S-, S,S-, and S,O-heterodonor ligands with a
binaphthalene framework
a
Wen Zhang, Qin Xu and Min Shi
b
a,b,
*
a
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science,
54 Fenglin Lu, Shanghai 200032, China
3
East China University of Science and Technology, 130 Mei Long Lu, Shanghai 200237, China
b
Received 22 July 2004; accepted 12 August 2004
Available online 17 September 2004
Abstract—Axially chiral P,S-heterodonor ligand L1 is effective in the asymmetric allylic substitution of 1,3-diphenylpropenyl acetate
with dimethyl malonate. Its bidentate coordination pattern to a Pd metal center with both P and S atoms has been unambiguously
established by X-ray diffraction and NMR spectroscopic analyses. Herein, we further disclose that axially chiral S,S-heterodonor
ligands L2–L4 are also effective in the same reaction to give the allylic alkylation product in moderate to good ee. However, the
corresponding S,O-heterodonor ligands are not as effective as the corresponding P,S- or S,S-heterodonor ligands in the same asym-
metric reaction.
ꢀ
2004 Elsevier Ltd. All rights reserved.
1
. Introduction
investigation on this type of P,S-heterodonor ligand L1
in the asymmetric allylic substitution of 1,3-diphenyl-
propenyl acetate are disclosed on the basis of the X-ray
crystal structure diffraction and NMR spectroscopic
data. We found that this ligand acted as a P,S-bidentate
ligand to palladium center and showed no hemilabile
character compared to that of BINPO (BINAP mono-
0
Chiral C -symmetric ligand 2,2 -bis(diphenylphosphino)-
2
,1 -binaphthyl (BINAP) A and C -symmetric ligand
1
0
1
1
2
(
0
-(diphenylphosphino)-1,1 -binaphthyl
2
(MOP)
0
B
X = OMe) possessing the axially chiral 1,1 -binaphthal-
ene framework have been widely utilized in asymmetric
catalysis (Fig. 1). Since then, significant effort has been
devoted to the design and synthesis of novel binaphthal-
ene-templated ligands. The representative examples are
the binaphthyl P,X-heterodonor ligands B where X
is a different heteroatom [X = NMe , SMe, AsPh ,
7
phosphine oxide). In addition, the asymmetric catalysis
of several other axially chiral S,S-, S,O-heterodonor
ligands in the same reaction has been disclosed in this
paper.
2
2
3
P(O)Ph , P(S)Ph , PAr ], such as phosphane–phosphite
2
2
2
4
ligand BINAPHOS C, and phosphine–pyridine ligand
5
0
0
D
(
derived from 2-amino-2 -hydroxy-1,1 -binaphthyl
NOBIN). Most of these axially chiral ligands are effec-
2. Results and discussion
2.1. Synthesis of ligands L1–L5
tive in the palladium-catalyzed asymmetric allylic substi-
tution of 1,3-diphenylpropenyl acetate with dimethyl
malonate in the presence of base. Herein, we report that
the P,S-heterodonor ligand L1 shown in Figure 1 is also
fairly effective in the palladium-catalyzed asymmetric
allylic substitution of 1,3-diphenylpropenyl acetate with
dimethyl malonate. In the mean time, the details of the
6
Axially chiral ligands L1–L5 were prepared from O-tri-
0
flated (R)-BINOL [(R)-(+)-1,1 -bi-2-naphthol] 1 accord-
8
ing to the Gladialiꢀs method (Scheme 1). Reduction of
compound 4 was carried out by HSiCl
of Et
in the presence
N in toluene at 120ꢁC to obtain P,S-heterodonor
3
3
ligand L1. The S,S-heterodonor ligands L2–L4 were eas-
ily prepared by heating compounds 9 and L1 with sulfur
at 120ꢁC. The S,O-heterodonor ligand L5 was synthe-
*
Corresponding author. Fax: +86 21 64166128; e-mail: mshi@
pub.sioc.ac.cn
sized by reduction of compound 6 with HSiCl in the
3
0
957-4166/$ - see front matter ꢀ 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2004.08.008

3162
W. Zhang et al. / Tetrahedron: Asymmetry 15 (2004) 3161–3169
O
C
O
PPh2
PPh2
Y
X
O
N
P
N
H
O
PPh
2
PPh2
PPh2
A
B
C
D
X= OMe, NMe , SMe, AsPh ,
2
2
Y=H, Me
P(O)Ph , P(S)Ph , PAr
2
2
2
S
C
O
NMe2
PPh2
L1
2 1
Figure 1. The structure of C -symmetric BINAP and C -symmetric binaphthyl P,X-heterodonor ligands.
NaOH, H O
OTf
OTf
Ph P(O)H, i-Pr NEt, Pd(OAc) /dppb
2
2
2
2
OTf
P(O)Ph2
o
o
25 C, 12 h
DMSO, 100 C, 14 h
1
2
S
C
S
C
OH
Me NC(S)Cl, NaH
O
NMe2
HSiCl , Et N, toluene
O
NMe2
2
3
3
P(O)Ph2
P(O)Ph2
o
P(O)Ph2
o
DMF, 90 C, 3 h
120 C, 12 h
3
L1
4
o
sulfur, toluene
Neat, 260-270 C
0 min.
o
120 C, 10 h
1
S
C
O
O
C
C
O
NMe2
S
HSiCl , Et N, toluene
S
NMe2
3
3
NMe2
P(S)Ph2
PPh2
P(O)Ph2
o
1
20 C, 6 h
9
L4
5
sulfur, toluene
LiAlH , THF
4
o
o
1
20 C, 10 h
25 C, 18 h
O
C
S
PPh2
SR
P(O)Ph2
RBr, MeOH, Et N
SH
P(O)Ph2
3
NMe2
o
25 C, 6-12 h
S
7
a: R= Me.
6
L5
7
b: R= CHPh2.
HSiCl , Et N, toluene
3
3
o
1
20 C, 6 h
SR
PPh2
S
sulfur, toluene
SR
PPh2
o
1
20 C, 10 h
8
8
a: R= Me.
b: R= CHPh2.
L2: R= Me.
L3: R= CHPh2.
Scheme 1. Synthesis of ligands L1–L5.

W. Zhang et al. / Tetrahedron: Asymmetry 15 (2004) 3161–3169
3163
presence of Et N and then upon heating with sulfur at
3
2.3. Other axially chiral S,S- or S,O-heterodonor ligands
used in asymmetric allylic alkylation
1
20ꢁC.
2.2. Catalytic asymmetric allylic alkylation of 1,3-diphen-
yl-2-propenyl acetate by chiral P,S-heterodonor ligand L1
Asymmetric allylic alkylation of 1,3-diphenylpropenyl
acetate with dimethyl malonate under the above condi-
tions were carried out in the presence of ligands L2–
L5 (Scheme 1). The results are summarized in Table 2.
First of all, we found that by using S,S-heterodonor lig-
and L2 as a chiral ligand in this reaction, the reaction
proceeded smoothly in a variety of solvents and addi-
tives (salts) to give the corresponding allylic substitution
product in good yields with low to moderate ee (Table 2,
entries 1–6). The highest ee was 31% in toluene in the
presence of KOAc with an (S)-configuration in 77%
yield (Table 2, entry 5). Using L3 as a chiral ligand in
this reaction in THF in the presence of either KOAc
or LiOAc, the achieved ee could reach 69% and 74%
with R configuration in 68% and 80% yield, respectively
(Table 2, entries 7 and 8). Using L4 as a chiral ligand
under the same conditions, the achieved ee was slightly
improved (Table 2, entries 9–14). In THF, the ee was
59% with an (R)-configuration in 70% yield in the pres-
ence of KOAc (Table 2, entry 9), while using LiOAc as
an additive, the ee was increased to 89% in 44% yield
(Table 2, entry 14). However, the reaction was sluggish
in the presence of axially chiral S,O-heterodonor ligand
L5 under similar conditions (Table 2, entry 15). Thus,
the S,S-heterodonor ligands are more effective than S,O-
heterodonor ligand in this Pd-catalyzed asymmetric C–
C bond forming reaction. Moreover, we also confirmed
that other axially chiral compounds 9, 4, 5, and 7a shown
in Scheme 1, did not catalyze the allylic alkylation of 1,3-
diphenylpropenyl acetate under the same conditions.
We found that this novel axially chiral P,S-heterodonor
ligand L1 was quite effective in the Pd(II)-catalyzed
asymmetric allylic substitution of 1,3-diphenylpropenyl
acetate with dimethyl malonate. The results are summa-
rized in Table 1. As can be seen from Table 1, the
achieved ee was 82% in 75% yield at ꢀ20ꢁC (Table 1,
entry 1). At 0ꢁC, 83% ee was realized in the presence
of ammonium salt Bu NCl (Table 2, entry 2). At ꢀ20
4
to ꢀ30ꢁC, the use of inorganic salts such as KOAc and
LiOAc did not significantly improve the enantioselectiv-
ities (Table 1, entries 3–6). In the presence of KOAc, the
achieved ee was 80% in 56% yield at ꢀ30ꢁC. In addition,
at ꢀ20ꢁC, the achieved ee was 64% in 94% yield in the
presence of KOAc and 83% ee in 80% yield in the pres-
ence of LiOAc, respectively. On the other hand, the sol-
vent and temperature effects have also been examined
under similar conditions with similar results were ob-
tained (Table 1, entries 7–13). When this reaction was
carried out in CH Cl in the presence of complex 10
2
2
(
see below) and AgOTf, a comparable result with 75%
ee was obtained (Table 1, entry 14). When NaCH-
CO Me) , prepared from dimethyl malonates with
(
2
2
NaH, was used as a nucleophile in this reaction, the
product was obtained with 78% ee in 43% yield (Table
1
, entry 15). The best result was obtained in THF in
the presence of LiOAc at ꢀ20ꢁC to give the adduct in
0% yield with 83% ee (Table 1, entry 6).
8
Table 1. The asymmetric allylic substitution catalyzed by Pd(II) in the presence of chiral P,S-ligand L1
3
[
Pd(η -C H )Cl] (2 mol%)
Ph
Ph
Ph
3
5
2
Ph
+
CH (CO Me)
2 2 2
L1 (6 mol%), BSA (3 equiv.),
OAc
CH(CO Me)
2 2
(
3 equiv.)
salt (10 mol%), solvent, r.t.
a
Yield (%)
b
c
Entry
Salt
—
Solvent
Temp. (ꢁC)
Time (h)
Ee
Absolute configuration
d
1
THF
THF
THF
THF
THF
THF
ꢀ20
0
17
44
2
75
74
91
94
56
80
86
74
69
95
68
79
64
12
43
82
83
45
64
80
83
80
83
75
76
68
71
72
75
78
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
2
3
4
5
6
7
8
9
4
Bu NCl
KOAc
KOAc
KOAc
LiOAc
0
ꢀ20
ꢀ30
ꢀ20
0
2
68
30
44
44
48
44
26.5
86
118
25
12
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
NCl
NCl
NCl
NCl
NCl
NCl
NCl
PhCH
CH CN
DMF
CH Cl
3
3
0
0
10
11
12
13
14
15
2
2
0
CHCl
CHCl
CHCl
3
3
3
10
0
ꢀ20
10
10
e
f
KOAc
—
2
CH Cl
THF
2
a
b
c
d
e
f
Isolated yields.
Determined by HPLC.
The absolute configuration was determined by comparing the sign of specific rotation with authentic sample reported in the literature.
No additive was used.
The complex 5 derived from L1 with Pd(PhCN)
2 2
Cl and AgOTf was used.
NaCH(CO Me) was used as an nucleophile.
2
2

3164
W. Zhang et al. / Tetrahedron: Asymmetry 15 (2004) 3161–3169
Table 2. The axially chiral S,S or S,O-heterodonor ligands L2–L5 in asymmetric allylic substitution
3
Ph
Ph
[Pd(η -C
3
H
5
)Cl]
2
(2 mol%)
Ph
Ph
+
CH
2
(CO
2 2
Me)
Ligand (6 mol%), BSA (3 equiv.), salt (10
mol%), solvent, r.t.
OAc
2 2
CH(CO Me)
(
3 equiv.)
S
C
O
C
SMe
S
SCHPh
S
2
O
NMe2
S
S
NMe2
S
PPh
2
PPh
2
PPh
2
PPh
2
L2
L3
L4
L5
a
Yield (%)
b
Ee (%)
c
Entry
Ligand
Salt
Solvent
Temp. (ꢁC)
Time (h)
Absolute configuration
1
2
3
4
5
6
7
8
9
L2
L2
L2
L2
L2
L2
L3
L3
L4
L4
L4
L4
L4
L4
L5
KOAc
LiOAc
KOAc
KOAc
KOAc
KOAc
KOAc
LiOAc
KOAc
KOAc
KOAc
KOAc
KOAc
LiOAc
KOAc
THF
THF
10
10
10
10
10
10
10
10
10
10
10
10
10
10
5
40
40
84
51
86
88
77
80
68
80
70
44
38
48
17
44
31
23
23
7
S
S
CH
CH
2
Cl
CN
2
12
12
S
3
4
S
PhCH
DMF
THF
THF
THF
3
36
36
31
24
69
74
59
27
4
S
S
26
26
R
R
R
R
R
R
R
R
R
80
82
10
11
12
13
14
15
CH
CH
2
Cl
CN
2
3
82
PhCH
DMF
THF
3
168
168
80
22
42
89
9
THF
168
a
b
c
Isolated yields.
Determined by HPLC.
The absolute configuration was determined by comparing the sign of specific rotation with authentic sample reported in the literature.
S
C
NMe
S
2
O
NMe
2
O
2 2
CH Cl
Cl
Cl
+
2 2
Pd(PhCN) Cl
Pd
PPh
2
P
Ph
2
L1
complex 10
1
3
1
1
3 3 2
H NMR (CDCl , TMS) δ 2.60, 2.70 (N(CH ) ).
H NMR (CDCl
1
3
, TMS) δ2.38, 3.04 (N(CH
, 85% H PO ) δ -13.71.
, TMS) δ38.07, 42.98 (N(CH
3
)
2
).
31P NMR (CDCl , 85% H PO ) δ 16.21.
P NMR (CDCl
3
3
4
3
3
4
3
13C NMR (CDCl , TMS) δ39.84, 42.22 (N(CH ) ),
C NMR (CDCl
66.56 (C=S).
3
3
)
2
),
3
3
2
1
180.73 (C=S).
1
31
13
Scheme 2. H NMR, P NMR, and C NMR analyses of L1 and complex 10.
3
1
2
Ph C H )(L1)]OTf, and Pd(L2)Cl
.4. Synthesis of complexes Pd(L1)Cl , [Pd(g -
nates to the metal center. H NMR spectra in CDCl
3
2
show that two methyl signals shift from 2.38 to
.04ppm in free ligand L1 to 2.60 and 2.70ppm in com-
2
3
3
2
3
In order to get straightforward evidence of the coordina-
tion pattern of L1 to Pd center, we decided to prepare a
Pd(II) complex from L1 with bis(benzonitrile)palladium
plex 10. These facts suggest that the chemical environ-
ment surrounding the methyl groups in complex 10
have changed. A similar phenomenon has been observed
9
13
dichloride [Pd(PhCN) Cl ] because it is known that
2
in C NMR spectra in CDCl with two methyl signals
3
2
sulfur and phosphorus atom can coordinate to Pd(II)
center to give a stable Pd(II) complex, which can be
subjected to the X-ray diffraction. The synthesis of the
shifting from 38.07 to 42.98ppm in free ligand L1 to
39.84 and 42.22ppm in complex 10 and the thiocarbonyl
signal (C@S group) shifts from 166.56ppm in free ligand
L1 to 180.73ppm in complex 10 as well. Thus, we believe
that the sulfur atom may coordinate to the palladium
metal center as well.
Pd(L1)Cl complex 10 was carried out by the reaction
2
of the appropriate amount of Pd(PhCN) Cl with
2
2
1
argon atmosphere (Scheme 2). The H, C, and
equiv of L1 in CH Cl at room temperature under an
2 2
P
NMR spectroscopic investigation on Pd(L1)Cl com-
1
13
31
The single crystals suitable for X-ray diffraction were
obtained by recrystallization from dichloromethane
2
plex 10 and free L1 in CDCl revealed that both phos-
3
1
0
phorus and sulfur atoms coordinated to the palladium
and toluene (1:4). The ORTEP drawing is shown in
Figure 2 in which L1 acts as a bidentate ligand to Pd(II)
center with both sulfur and phosphorus atoms provid-
ing a nine-membered chelate ring with an irregular,
partially boat-like conformation. The bond distances
3
1
center. For free ligand L1, P NMR signal appears at
13.71ppm, while for complex 10 this signal appears
ꢀ
at 16.21ppm. This drastic chemical shift change pro-
vides an indication that the phosphorus atom coordi-

W. Zhang et al. / Tetrahedron: Asymmetry 15 (2004) 3161–3169
3165
Me
Pd
SMe
S
Cl
Cl
2 2
CH Cl
+
2
Pd(PhCN) Cl2
S
P(S)Ph
2
PPh
2
L2
3
, TMS) δ 2.31 (SCH ).
complex 12
1
3
H NMR (CDCl
1
3
1
H NMR (CDCl
1
3
, TMS) δ 2.98 (SCH
3
).
P NMR (CDCl
3
, 85% H
3
PO
4
) δ 46.35.
3
P NMR (CDCl
3
, 85% H PO ) δ 40.74.
3
4
1 31
Scheme 4. H NMR and P NMR analyses of L2 and complex 12.
The coordination pattern of ligand L2 to Pd center was
investigated by H NMR and P NMR spectroscopic
1
31
studies in CDCl . The signals of the (S)-methyl and
3
phosphorus atom showed significant shifts after the
addition of Pd(PhCN) Cl in CDCl as compared with
2
2
3
free ligand L2 (Scheme 4) with complex 12 presumably
formed (Scheme 4). These results suggest that the S,S-
heterodonor ligand can coordinate to the Pd metal cen-
ter by two sulfur atoms as a bidentate ligand in a similar
way as P,S-heterodonor ligand described above to cata-
lyze the asymmetric C–C bond forming reaction,
although in some cases they are not as effective as the
P,S-heterodonor ligand.
Figure 2. The ORTEP drawing of complex 10.
˚
Table 3. Selected bond lengths (A) and bond angles (deg) for
Pd(L1)Cl
2
complex 10
Bond lengths
Bond angles
Pd–P
Pd–S
2.2585 (10)
2.3012 (11)
2.3539 (12)
2.2966 (11)
P–Pd–S
95.70 (4)
89.12 (4)
85.33 (4)
89.68 (4)
P–Pd–Cl (2)
S–Pd–Cl (1)
Cl (2)–Pd–Cl (1)
2.5. Axially chiral P,S-heterodonor ligand L1 in asym-
metric allylic amination
Pd–Cl (1)
Pd–Cl (2)
Asymmetric allylic amination of 1,3-diphenylpropenyl
acetate with benzylamine to form carbon–nitrogen bond
is a useful method in organic synthesis. However,
˚
of Pd–S and Pd–P are 2.3012 and 2.2585A, respectively,
which are in the normal region (Table 3). The stronger
13
1
1
amines acting as nucleophiles in an asymmetric allylic
substitution have proven to be a challenge because the
N-nucleophiles are less reactive than malonate in the
1
2
trans influence of the phosphorus atom (vs the sulfur
atom in the thiocarbonyl group) is reflected in the differ-
ence of the Pd–Cl bond distances trans to the phospho-
rus atom (2.3539A) and trans to the sulfur atom
(
14,15
presence of base.
1
Thus, the allylic amination of
,3-diphenylpropenyl acetate with benzylamine was also
˚
˚
2.2966A).
examined by the axially chiral P,S-heterodonor ligands
L1 under similar conditions. Unfortunately, we found
that this chiral ligand is ineffective in allylic amination
The synthesis of complex 11 was also carried out via
reaction of 1,3-diphenylallylpalladium chloride dimmer
with L1 and AgOTf in dichloromethane at room tem-
(
Table 4, entries 1–7).
3
perature to produce [Pd(g -Ph C H )(L1)]OTf (Scheme
2
3
3
3
structure of this complex in solution. The P NMR
). NMR spectroscopy allowed us to determine the
3. Conclusion
3
1
spectrum in the CDCl of complex 11 showed one signal
3
We have found a novel axially chiral P,S-heterodonor
ligand L1 is quite effective in an asymmetric C–C bond
forming reaction. Their bidentate coordination patterns
to the Pd metal center with P and S atoms have been
at 20.66ppm. This fact suggests that only one isomer of
the palladium allyl complex can be obtained in solution.
1
The H NMR spectrum of 11 in CDCl solution was
3
also consistent with the existence of one isomer. The sig-
nals of two methyl groups were at 2.58 and 2.87ppm
1
unambiguously established by X-ray diffraction and H
31
13
NMR, P NMR, and C NMR analyses. Herein, we
have further disclosed that axially chiral S,S-heterodo-
nor ligands L2–L4 are also fairly effective in the same
reaction to give the allylic alkylation product in moder-
ate to good ee. While, the corresponding S,O-hetero-
donor ligands are not as effective as the corresponding
P,S- or S,S-heterodonor ligands in this reaction. Based
on these results, we are able to plan how to exploit these
(
Scheme 3).
S
C
NMe
2
Ph
Ph
O
NMe2
2
O
S
Pd
CH
2
Cl
2
3
+
[Pd(η -Ph
2
C
3
H
3
)Cl]
2
PPh
AgOTf
P
axially chiral C -symmetric P,S- or S,S-heterodonor lig-
1
Ph
2
ands in other asymmetric catalysis and synthesize further
these kinds of ligands in order to seek out more effective
and stereoselective chiral ligands in catalytic asymmet-
ric reactions. Work along this line is currently in
progress.
L1
H NMR (CDCl , TMS) δ2.38, 3.04 (N(CH
complex 11
1
1
3
3
)
2
).
H NMR (CDCl
P NMR (CDCl
3
, TMS) δ 2.58, 2.87 (N(CH
, 85% H PO ) δ 20.66.
3 2
) ).
3
1
31
P NMR (CDCl
3
, 85% H
3
PO
4
) δ -13.71.
3
3
4
1
31
Scheme 3. H NMR and P NMR analyses of L1 and complex 11.

3166
W. Zhang et al. / Tetrahedron: Asymmetry 15 (2004) 3161–3169
Table 4. Allylic amination of 1,3-diphenylpropenyl acetate with benzylamine catalyzed by Pd(II) and chiral ligand L1
3
Ph
Ph
OAc
[Pd(η -C H )Cl] (2 mol%)
Ph
3
5
2
Ph
+
BnNH2
Ligand (6 mol%), solvent, r.t.
(
2 equiv.)
NHBn
a
Yield (%)
b
Ee (%)
c
Entry
Ligand
Solvent
Temp. (ꢁC)
Time (h)
Absolute configuration
1
2
3
4
5
6
7
L1
L1
L1
L1
L1
L1
L1
CH
ClCH
CH
2
Cl
2
10
10
10
10
10
10
10
48
56
12
20
26
23
0
R
2
CH
2
Cl
9.4
4
R
3
CN
56
S
DMF
CHCl
THF
61
7
—
—
—
—
d
d
d
3
168
168
168
NR
NR
NR
—
—
—
PhCH
3
a
b
c
Isolated yields.
Determined by HPLC.
The absolute configuration was determined by comparing the sign of specific rotation with authentic sample reported in the literature.
No reaction took place.
d
0
4. Experimental
4.1.3. (R)-(ꢀ)-2-(Diphenylphosphinyl)-2 -hydroxybinaph-
2
b
1
thyl 3. This is a known compound.
H NMR
4
.1. General
(CDCl , 300MHz, TMS): d 6.41–7.95 (m, 22H,
3
3
1
Ar); P NMR (CDCl , 121MHz, 85% H PO ): d 31.97.
3
3
4
Melting points were obtained with a micro melting point
apparatus and are uncorrected. Optical rotations were
0
0
4.1.4. (R)-(ꢀ)-2-(Diphenylphosphinyl)-1,1 -binaphthyl-2 -
ol-N,N-dimethylthiocarbamate 4. This is a known
determined in a solution of CHCl at 20ꢁC by using a
3
8
20
D
8
polarimeter; [a] -values are given in units of
compound. ½aꢁ ¼ ꢀ142:8 (c 1.155, CHCl ), {lit.
D
3
ꢀ
1
2
degcm g . Infrared spectra were measured on a
ꢀ1
25
D
1
1
0
spectrometer. H NMR spectra were recorded for a
½aꢁ ¼ þ149 (c 1, CHCl ) for (S)-enantiomer};
H
3
1
NMR (CDCl , 300MHz, TMS): d 2.97 (s, 3H, CH ),
3 3
31
solution in CDCl with tetramethylsilane (TMS) as the
3
3.05 (s, 3H, CH ), 6.83–8.05 (m, 22H, Ar); P NMR
3
3
1
internal standard. P NMR spectra were recorded at
21MHz for a solution in CDCl with 85% H PO as
(CDCl , 121MHz, 85% H PO ): d 27.80.
3
3
4
1
3
3
4
0
the external reference. J-values are given in Hz. Mass
spectra were recorded with an HP-5989 instrument
and HRMS was measured by a Finnigan MAT mass
spectrometer. The organic solvents used were dried by
standard methods when necessary. All solid compounds
reported in this paper gave satisfactory CHN micro-
analyses and HRMS values. Commercially obtained
reagents were used without further purification. All
reactions were monitored by TLC. Flash column chro-
matography was carried out using silica gel under pres-
sure. All alkylation and amination experiments were
performed under an argon atmosphere using standard
Schlenk techniques. The enantiomeric excesses of di-
methyl(1,3-diphenyl-2-propen-1-yl)malonate and 1-benz-
ylamine-1,3-diphenylprop-2-ene were determined by
chiral HPLC analyses and the absolute configuration
of the major enantiomer assigned according to the sign
4.1.5. (R)-(ꢀ)-2-(Diphenylphosphanyl)-1,1 -binaphthyl-
0
2 -ol-N,N-dimethylthiocarbamate L1. To a solution
of (R)-(ꢀ)-2-(diphenylphosphinyl)-1,1 -binaphthyl-2 -ol-
0
0
N,N-dimethylthiocarbamate 4 (500mg, 1.0mmol) in tolu-
ene (10mL) containing Et N (8.4mL) was stirred at
3
0ꢁC. HSiCl (0.85mL, 6.2mmol) was then added and
3
the reaction mixture stirred at 120ꢁC for 12h. After
cooling to room temperature, 10% HCl (10mL) was
added and the organic phase was separated. The aque-
ous layer was extracted with ether (3 · 20mL), the com-
bined organic phase dried over anhydrous Na SO , and
2
4
the solvent evaporated under reduced pressure. The res-
idue was purified by a flash chromatography (eluent:
PE/EtOAc = 10:1) to give L1 as a white solid. 298mg,
20
yield 55%, mp: 79–81ꢁC; ½aꢁ ¼ ꢀ17:3 (c 0.96, CHCl );
D
3
IR (CH Cl ): m 1712, 1543, 1436, 1396, 1289, 1219, 1170,
2
2
ꢀ
1
1
818, 518cm ; H NMR (CDCl , 300MHz, TMS): d
2.38 (s, 3H, CH ), 3.04 (s, 3H, CH ), 6.85–8.02 (m,
22H, Ar); C NMR (CDCl , 75MHz, TMS): d 38.07,
3
0
of the specific rotation. (R)-(+)-1,1 -Bi-2-naphthol was
purchased from Aldrich.
3
3
1
3
3
4
1
1
1
6
5
1
2.98, 123.80, 125.65, 126.37, 126.59 (d, JC–P = 1.3Hz),
27.52 (d, JC–P = 22.4Hz), 128.29 (d, JC–P = 2.3Hz),
28.35 (d, JC–P = 6.6Hz), 128.46 (d, JC–P = 7.7Hz),
0 0
(R)-2,2 -Bis(trifluoromethanesulfonyl)oxy-1,1 -
4.1.1.
binaphthyl 1. This is a known compound.
2
b
1
H
28.50, 128.52 (d, JC–P = 19.4Hz), 128.53 (d, JC–P
.3Hz), 128.55 (d, JC–P = 2.5Hz), 128.61 (d, JC–P
=
=
NMR (CDCl , 300MHz, TMS): d 7.24–8.16 (m, 12H,
3
Ar).
.4Hz), 128.65, 128.73, 130.38 (d, JC–P = 2.0Hz),
31.55, 133.07 (d, JC–P = 7.1Hz), 133.71 (d, JC–P
=
=
=
=
0
4
methanesulfonyl)oxy]-1,1 -binaphthyl 2. This is
.1.2.
(R)-(+)-2-(Diphenylphosphinyl)-2 -[(trifluoro-
a
H NMR (CDCl , 300MHz,
19.3Hz), 133.75 (d, JC–P = 0.8Hz), 133.97 (d, JC–P
19.6Hz), 134.15 (d, JC–P = 2.6Hz), 136.23 (d, JC–P
11.9Hz), 138.03 (d, JC–P = 13.1Hz), 138.26 (d, J
13.7Hz), 140.92, 141.38, 149.75, 166.56; P NMR
(CDCl , 121MHz, 85% H PO ): d ꢀ13.71; MS (EI)
0
2
b
1
known compound.
3
C–P
3
1
31
TMS): d 6.98–8.02 (m, 22H, Ar); P NMR (CDCl3,
21MHz, 85% H PO ): d 29.60.
1
3
4
3
3
4

W. Zhang et al. / Tetrahedron: Asymmetry 15 (2004) 3161–3169
3167
+
m/e 541 (M , 2.22), 453 (10.74), 437 (100), 268 (9.31),
containing Et N (8.4mL) was stirred at 0ꢁC. HSiCl
3
3
1
83 (4.36); HRMS (EI) calcd for C H ONSP requires:
3
(0.85mL, 6.2mmol) was then added and the reaction
mixture stirred at 120ꢁC for 6h. After cooling to room
temperature, 10% HCl (10mL) was added and the
organic phase separated. The aqueous layer was
extracted with ether (3 · 20mL), the combined organic
phase dried over anhydrous Na SO , and the solvent
5
28
5
41.1629, found: 541.1639.
0
0
4
.1.6. (R)-(+)-2-(Diphenylphosphinyl)-1,1 -binaphthyl-2 -
5. This is
known compound. ½aꢁ ¼ þ11:3 (c 1.05, CHCl ),
thiol-N,N-dimethylthiocarbamate
a
8
20
D
3
1
2
4
8
25
{
lit. ½aꢁ ¼ ꢀ5:7 (c 1, CHCl ) for (S)-enantiomer}; H
evaporated under reduced pressure. The residue was
purified by flash chromatography (eluent: PE/
EtOAc = 10:1) to give 8b as a white solid. 257mg, 39%
yield. This compound was very sensitive to air and can
be easily oxidized to phosphine oxide. Thus, the product
D
3
NMR (CDCl , 300MHz, TMS): d 2.75 (s, 6H, 2CH ),
3
3
3
.80–8.10 (m, 22H, Ar); P NMR (CDCl , 121MHz,
1
6
3
8
5% H PO ): d 29.43.
3
4
0
0
1
4
.1.7. (R)-(+)-2-(Diphenylphosphinyl)-1,1 -binaphthyl-2 -
8
always contained some amount of phosphine oxide. H
NMR (CDCl , 300MHz, TMS): d 5.52 (s, 0.77H, CH),
20
D
thiol 6. This is a known compound. ½aꢁ ¼ þ79:9 (c
3
8
25
.125, CHCl ), {lit. ½aꢁ ¼ ꢀ42:3 (c 1, CHCl ) for the
31
5.70 (s, 1H, CH), 6.61–8.01 (m, 57H, Ar); P NMR
1
(
3
3
D
3
1
S)-enantiomer}; H NMR (CDCl , 300MHz, TMS): d
(CDCl , 121MHz, 85% H PO ): d ꢀ13.30, 30.14.
3
3
3
4
3
.48 (s, 1H, SH), 6.82–8.04 (m, 22H, Ar); P NMR
1
0
(
CDCl , 121MHz, 85% H PO ): d 28.88.
4.1.12. (R)-(+)-2-(Diphenylphosphinothioyl)-2 -methyl-
sulfanyl-1,1 -binaphthalenyl L2. To
3
3
4
0
a
solution of
0
0
0
4
.1.8. (R)-(+)-2-(Diphenylphosphinoyl)-2 -methylsulfan-
(R)-(+)-2-(diphenylphosphanyl)-2 -methylsulfanyl-1,1 -bi-
naphthalenyl 8a (266mg, 0.55mmol) in toluene (5mL)
was added sulfur (24.6mg, 0.77mmol, 1.4equiv) and
the reaction mixture stirred at room temperature for
1h and then heated to 120ꢁC for 10h. After cooling to
room temperature, the solvent was evaporated under
reduced pressure and the residue purified by flash chro-
matography (eluent: PE/EtOAc = 4:1) to give L2 as a
0
yl-1,1 -binaphthalenyl 7a. This compound was pre-
pared from 7 as the similar procedure described in the
8
20
D
8
literature. ½aꢁ ¼ þ138:1 (c 0.605, CHCl ), {lit.
3
25
½
aꢁ ¼ ꢀ126:2 (c 0.5, CHCl ) for the (S)-enantiomer};
D
3
1
H NMR (CDCl , 300MHz, TMS): d 2.29 (s, 3H,
3
3
CH ), 6.86–8.02 (m, 22H, Ar); P NMR (CDCl3,
1
3
1
21MHz, 85% H PO ): d 29.39.
3 4
white solid. 218mg, 77% yield; mp: 98–99ꢁC;
0
20
4.1.9. (R)-(+)-2-(Diphenylphosphinoyl)-2 -benzhydrylsulfan-
yl-1,1 -binaphthalenyl 7b. To a solution of (R)-(+)-2-
½aꢁ ¼ þ163:7 (c 0.865, CHCl ); IR (CH Cl ): m 2685,
D
3
2
2
0
ꢀ1
2306, 1422, 1162, 896, 403cm ; H NMR (CDCl ,
3
1
0
0
(
diphenylphosphinyl)-1,1 -binaphthyl-2 -thiol (900
mg, 1.85mmol) in methanol (10mL), Et N (6mL) with
methyl iodide (0.12mL, 2mmol) was added. The reac-
tion mixture was stirred for 5h at room temperature.
The solvent was removed under reduced pressure and
the residue dissolved in CH Cl (10mL). The organic
6
300MHz, TMS): d 2.31 (s, 3H, CH ), 6.88–8.01 (m,
3
31
22H, Ar); P NMR (CDCl , 121MHz, 85% H PO ):
3 3 4
3
+
d 46.35; MS (EI) m/e 517 (M +1, 1.55), 502 (3.04),
470 (100), 438 (7.78), 282 (16.79), 183 (9.31); HRMS
(EI) calcd for: C H PS requires: 516.1135, found;
3
3
25
2
516.1152.
2
2
phase was washed with water (3 · 10mL) and dried over
anhydrous Na SO . The solvent was evaporated under
2
4
0
4.1.13. (R)-(+)-2-(Diphenylphosphinothioyl)-2 -benzhydr-
ylsulfanyl-1,1 -binaphthalenyl L3. This compound was
reduced pressure to give a crude product, which was
purified by a flash chromatography (eluent: PE/
EtOAc = 2:1) to give 7b as a white solid: 294mg, 45%
0
0
prepared from (R)-(+)-2-(diphenylphosphanyl)-2 -benz-
0
20
hydrylsulfanyl-1, 1 -binaphthalenyl 8b in a similar way
to that described above. White solid, yield 87%. Mp:
yield; mp: 119–120ꢁC; ½aꢁ ¼ þ42:7 (c 1.1, CHCl ); IR
D
3
ꢀ
1
1
(
CH Cl ) m 1422, 1163, 896cm ; H NMR (CDCl ,
20
D
2
2
3
1
07–109ꢁC; ½aꢁ ¼ þ42:8 (c 0.835, CHCl3); IR
3
3
3
00MHz, TMS) d 5.52 (s, 1H, CH), 6.80–8.02 (m,
ꢀ1
1
3
1
(CH Cl ): m 1437, 1161, 896cm ; H NMR (CDCl ,
2
2
3
2H, Ar); P NMR (CDCl , 121MHz, 85% H PO ) d
3
3
4
+
0.11; MS (EI) m/e 652 (M , 12.57), 485 (30.68), 453
300MHz, TMS) d 5.40 (s, 1H, CH), 6.81–8.00 (m,
31
2H, Ar); P NMR (CDCl , 121MHz, 85% H PO ):
3
3 3 4
+
(
(
18.26), 282 (21.22), 201 (100), 167 (77.42); HRMS
ESI) calcd for C H OPSNa (M +Na) requires:
+
d 46.66; MS (ESI) m/e 669 (M +1); HRMS (ESI) calcd
4
8
33
+
for C H PS Na (M +Na) requires: 691.1649, found:
4
5
33
2
6
75.1852, found: 675.1882.
691.1654.
0
4.1.10. (R)-(+)-2-(Diphenylphosphanyl)-2 -methylsulfa-
nyl-1,1 -binaphthalenyl 8a. This compound was pre-
0
0
4.1.14. (R)-(ꢀ)-2-(Diphenylphosphinothioyl)-1,1 -binaph-
8
0
pared from 8a as described in the25 literature.
thyl-2 -ol-N,N-dimethylthiocarbamate L4. This com-
pound was prepared from (R)-(ꢀ)-2-(diphen-
2
0
8
½
aꢁ ¼ þ49:8 (c 0.535, CHCl ), {lit. ½aꢁ ¼ ꢀ52:6 (c
D
3
D
.5, CHCl ) for the (S)-enantiomer}; H NMR (CDCl ,
1
0
0
0
ylphosphanyl)-1,1 -binaphthyl-2 -ol-N,N-dimethylthio-
carbamate L1 in a similar way to that described above.
3
3
3
2
00MHz, TMS): d 2.31 (s, 3H, CH ), 6.68–7.99 (m,
3
3
2H, Ar); P NMR (CDCl , 121MHz, 85% H PO ):
1
20
D
White solid, yield 88%; mp: 108–109ꢁC; ½aꢁ ¼ ꢀ165:5
3
3
4
dꢀ13.07.
(c 0.785, CHCl ); IR (CH Cl ): m 1536, 1437, 1220,
3
2
2
ꢀ
1
1
1
168, 896, 401cm
;
H NMR (CDCl , 300MHz,
TMS): d 3.03 (s, 3H, CH ), 3.06 (s, 3H, CH ), 6.72–
3 3
31
7.90 (m, 22H, Ar); P NMR (CDCl , 121MHz, 85%
H PO ): d 45.75; MS (EI) m/e 573 (M , 0.99), 501
(100), 485 (31.77), 469 (97.84), 217 (38.87), 88 (43.98);
3
0
4.1.11. (R)-(+)-2-(Diphenylphosphanyl)-2 -benzhydry-l-
sulfanyl-1,1 -binaphthalenyl 8b. A solution of (R)-(+)-
0
3
0
0
+
2-(diphenylphosphinoyl)-2 -methylsulfanyl-1,1 -binaph-
thalenyl 7b (652mg, 1.0mmol) in toluene (10mL)
3
4

3168
W. Zhang et al. / Tetrahedron: Asymmetry 15 (2004) 3161–3169
+
HRMS (ESI) calcd for C H ONS PNa (M +Na)
requires: 596.1246, found: 596.1242.
11.7Hz, 1H, allyl), 6.39–6.51 (m, 4H, Ar), 6.68–6.78
(m, 5H, Ar), 7.04–7.67 (m, 18H, Ar), 7.88–7.94 (m,
3
5
28
2
3
H, Ar), 8.21 (d, J = 8.1Hz, 1H, Ar), 8.46 (d,
J = 8.7Hz, 1H, Ar). P NMR (CDCl , 121MHz, 85%
0
31
4
.1.15. (R)-(+)-2-(Diphenylphosphanyl)-1,1 -binaphthyl-
3
0
2 -thiol-N,N-dimethylthiocarbamate 9. This compound
was prepared from (R)-(+)-2-(diphenylphosphinyl)-
,1 -binaphthyl-2 -thiol-N,N-dimethylthiocarbamate
H PO ): d 20.66.
3
4
0
0
1
5
4.4. The preparation of complex 12 from ligand L2 with
PdCl (PhCN)
20
in a similar way to that described above. ½aꢁ ¼ þ14:8
D
2
2
8
25
D
(
(
2
c 0.205, THF), {lit. ½aꢁ ¼ ꢀ15 (c 1, THF) for the
1
S)-enantiomer}, H NMR (CDCl , 300MHz, TMS) d
This complex was prepared in the similar method as that
described above. H NMR (CDCl , 300MHz, TMS): d
2.98 (s, 3H, Me), 6.18–8.16 (m, 22H, Ar); P NMR
3
3
.66 (s, 6H, 2CH ), 6.86–7.98 (m, 22H, Ar); P NMR
1
1
3
3
31
(
CDCl , 121MHz, 85% H PO ) d ꢀ14.45.
3
3
4
(CDCl , 121MHz, 85% H PO ): d 40.74.
3
3
4
0
4
.1.16. (R)-(+)-2-(Diphenylphosphinothioyl)-1,1 -binaph-
thyl-2 -thiol-N,N-dimethylthiocarbamate L5. This com-
pound was prepared from (R)-(+)-2-(diphen-
0
4.5. Typical reaction procedure of Pd-catalyzed asym-
metric allylation of 1,3-diphenylpropenyl acetate with
dimethyl malonate
0
0
ylphosphanyl)-1,1 -binaphthyl-2 -thiol-N,N-dimethylthio-
carbamate 9 in the similar way to that described above.
2
0
3
White solid, yield 69%; mp: 206–207ꢁC; ½aꢁ ¼ þ6:4 (c
To a solution of allyl chloride palladium dimer [Pd(g -
C H )Cl] (1.8mg, 0.005mmol, 2mol%) in solvent
D
ꢀ
1
1
.29, CHCl ); IR (CH Cl ): m 1664, 1437, 1097cm
;
3
2
2
3
5
2
1
H NMR (CDCl , 300MHz, TMS): d 2.76 (s, 6H,
(1.0mL) was added enantiomerically pure ligand L1
(0.015mmol, 6mol%) under an argon atmosphere, and
the reaction mixture stirred at room temperature for
30min. A solution of 1,3-diphenylpropenyl acetate
(63mg, 0.25mmol) in solvent (0.5mL) was added, fol-
lowed by the addition of salt (0.025mmol, 10mol%).
The reaction solution was then stirred for a further
5min under certain temperature (see Tables 1–3). After-
wards, dimethyl malonate (0.09mL, 0.75mmol, 3equiv)
and N,O-bis(trimethylsilyl) acetamide (BSA) (0.19mL,
0.75mmol, 3equiv) were added and the reaction moni-
tored by TLC plates until 1,3-diphenylpropenyl acetate
was consumed completely. The reaction was quenched
3
3
1
CH ), 6.98–7.96 (m, 22H, Ar); P NMR (CDCl3,
2
1
(
(
(
3
21MHz, 85% H PO ): d 45.85; MS (EI) m/e 574
3
4
+
M +1, 0.88), 501 (100), 469 (97.96), 437 (22.64), 282
27.16), 217 (23.18); HRMS (EI) calcd for C H S P
2
M ꢀC(O)NMe ) requires: 501.0901, found: 501.0875.
3
22 2
+
2
4.2. The preparation of complex 10 from ligand L1 with
PdCl (PhCN)
2
2
Ligand L1 (54mg, 0.1mmol) and bis(benzonitrile)palla-
dium dichloride (38mg, 0.1mmol) were dissolved in
dichloromethane (1.0mL) under an argon atmosphere.
Degassed hexane (5.0mL) was then slowly added at
room temperature, which led to the precipitation of
the formed complex. The mother liquor was filtered
off, and the precipitate washed with hexane
by the addition of saturated NH Cl aqueous solution
4
and the product extracted with CH Cl (3 · 10mL).
The combined organic layers were dried over anhydrous
Na SO , filtered, and concentrated in vacuo to yield the
2
2
2
4
(
2 · 1.0mL) to afford complex (R)-(+)-10 as an orange
crude product, which was purified by flash chromato-
graphy on silica gel (eluent: PE/EtOAc = 20:1) to furnish
dimethyl(1,3-diphenyl-2-propen-1-yl)malonate as a col-
powder; 53mg, 74% yield. The single crystals for
X-ray diffraction were obtained by recrystallization
from dichloromethane and toluene (1:4). Mp: >300ꢁC,
1
orless solid. H NMR (CDCl , 300MHz, TMS): d 3.52
3
20
½
aꢁ ¼ þ206 (c 0.105, CHCl ); IR (neat): m 1570, 1434,
(s, 3H, Me), 3.70 (s, 3H, Me), 3.94 (d, J = 16.5Hz, 1H,
CH), 4.27 (dd, J = 8.4, 16.8Hz, 1H, CH), 6.32 (dd,
J = 8.4, 15.6Hz, 1H, CH), 6.48 (d, J = 15.6Hz, 1H,
CH), 7.19–7.33 (m, 10H, Ar). The enantiomeric excess
D
405, 1282, 1212, 1198, 748, 696cm
3
ꢀ
1
1
1
;
H NMR
(
3
1
CDCl , 300MHz, TMS): 2.60 (s, 3H, CH ), 2.70 (s,
3 3
3
H, CH ), 6.52–8.27 (m, 22H, Ar); P NMR (CDCl3,
1
3
1
6
21MHz, 85% H PO ): d 16.04; MS (ESI) m/e 736.9
was determined by HPLC (Chiralcel OD, eluent: n-
hexane/i-propanol = 80:20), flow rate: 0.7mL/min,
retention times: 18.0min (R), 19.3 min (S).
3
4
þ
(
MNH ). Anal. Calcd for C H Cl NOPSPdÆ1/
4
35 28 2
2
Found: C, 56.92; H, 4.12; N, 1.44%.
C H Æ2/3CH CL requires: C, 57.25; H, 4.09; N, 1.70.
7 8 2 2
4
.6. Typical reaction procedure of Pd-catalyzed asym-
4
.3. The preparation of complex 11
metric allylic amination of 1,3-diphenylpropenyl acetate
with benzylamine
To a Schlenk flask containing L1 (27mg, 0.05mmol) in
CH Cl (2mL) was added [(1,3-diphenylpropen-
3
To a solution of allyl chloride palladium dimmer [Pd(g -
2
2
yl)PdCl] (17mg, 0.025mmol), and the reaction allowed
2
C H )Cl] (1.8mg, 0.005mmol, 2mol%) in solvent
3
5
2
to stir for 1h. The solution was transferred by cannula
into a flask containing AgOTf (13mg, 0.05mmol) in
CH Cl (1mL) and stirred for 1h in the absence of light.
(1.0mL) was added enantiomerically pure ligand L1
(0.015mmol, 6mol%) under an argon atmosphere, and
the reaction mixture stirred at room temperature for
30min. A solution of 1,3-diphenylpropenyl acetate
(63mg, 0.25mmol) in solvent (0.5mL) was added and
the reaction stirred for a further 5min at room temper-
ature. Then, benzylamine (0.63mL, 0.5mmol, 2equiv)
was added into the reaction mixture and the reaction
2
2
The reaction was filtered and concentrated in vacuo to
obtain an orange power. 40mg, 81% yield. H NMR
1
(
allyl), 2.58 (s, 3H, Me), 2.87 (s, 3H, Me), 3.36 (dd,
CDCl , 300MHz, TMS): d 2.37 (d, J = 12.0Hz, 1H,
3
J = 11.4, 11.1Hz, 1H, allyl), 2.37 (dd, J = 12.3,

W. Zhang et al. / Tetrahedron: Asymmetry 15 (2004) 3161–3169
3169
monitored by TLC plates until 1,3-diphenylpropenyl
acetate was consumed completely or the time as indi-
cated in Table 4. The reaction was quenched by the
Lett. 1998, 9, 391; (d) Ligand X = P(O)Ph
S.; Pulacchini, S.; Fabbri, D.; Manassero, M.; Sansoni, M.
Tetrahedron: Asymmetry 1998, 9, 391; (e) Ligand
2
. See: Gladiali,
2
X = P(S)Ph . See: Faller, J. W.; Wilt, J. C.; Parr, J. Org.
addition of saturated NH Cl aqueous solution and the
4
Lett. 2004, 6, 1301; (f) TolBINAP. See: Takaya, H.;
Mashima, K.; Koyano, K.; Yagi, M.; Kumobayashi, H.;
Taketomi, T.; Akutagawa, S.; Noyori, R. J. Org. Chem.
product extracted with CH Cl (3 · 10mL). The com-
2
2
bined organic layers were dried over anhydrous Na SO ,
2
4
filtered and concentrated in vacuo to yield the crude
product, which was purified by a flash chromatography
on silica gel (eluent: PE/EtOAc = 20:1) to yield 1-benzyl-
1
986, 51, 629.
4
. BINAPHOS ligand, see: (a) Sakai, N.; Takaya, H. J. Am.
Chem. Soc. 1993, 115, 5326; (b) Nozaki, K.; Takaya, H. J.
Am. Chem. Soc. 1997, 119, 4413; (c) Horiuchi, T.; Takaya,
H. J. Org. Chem. 1997, 62, 4285; (d) Nozaki, K.; Komaki,
H.; Kawashima, Y.; Hiyama, T.; Matsubara, T. J. Am.
Chem. Soc. 2001, 123, 534.
amine-1,3-diphenylprop-2-ene as
a
colorless oil.
1
H NMR (CDCl , 300MHz, TMS): d 1.65 (br, 1H,
3
NH), 3.79 (dd, J = 13.5, 16.2Hz, 2H, CH ), 4.40 (d,
J = 7.2Hz, 1H, CH), 6.32 (dd, J = 7.5, 15.9Hz, 1H,
CH), 6.58 (d, J = 15.9Hz, 1H, CH), 7.21–7.45 (m,
2
5
6
7
. Hu, X.; Chen, H.; Zhang, X. Angew. Chem., Int. Ed. 1999,
3
8, 3518.
1
HPLC (Chiralcel OJ,
5H, Ar). The enantiomeric excess was determined by
1
. Catalytic Asymmetric Synthesis; Ojima, I., Ed.; Wiley:
VCH, 2000; Chapter 8E, p 593, by Trost, B. M.; Lee, C.
. Gladiali, S.; Taras, R.; Ceder, R. M.; Rocamora, M.;
Muller, G.; Solans, X.; Fromt-Bardia, M. Tetrahedron:
Asymmetry 2004, 15, 1477.
6
eluent: n-hexane/i-propa-
nol = 90:10), flow rate: 0.7mL/min, retention times:
4.5min (S), 17.9min (R).
1
8. Gladiali, S.; Medici, S.; Pirri, G.; Pulacchini, S.; Fabbri,
D. Can. J. Chem. 2001, 79, 670.
9. Doyle, J. R. Inorg. Synth. 1960, 6, 218.
Acknowledgements
We thank the State Key Project of Basic Research (Pro-
ject 973) (No. G2000048007), Shanghai Municipal Com-
mittee of Science and Technology, Chinese Academy of
Sciences (KGCX2-210-01), and the National Natural
Science Foundation of China (20025206, 20390050,
and 20272069) for financial support.
10. The X-ray crystal data of complex 5: C43H38NOPCl PdS,
4
formula weight: 895.97, temperature: 293(2)K, crystal
system, space group: Orthorhombic, P2(1)2(1)2(1), unit
˚
˚
cell dimensions: a = 11.7766(6)A, b = 13.7252(7)A,
˚
c = 25.4436(13)A, a = 90ꢁ, b = 90ꢁ, 3c = 90ꢁ, V =
˚
112.6(4)A , Zvalue = 4, Dcalc = 1.447g/cm , F0 0 0 = 1824.
3
4
Crystal size: 0.560 · 0.255 · 0.136mm. Data/restraints/
parameters= 9413/6/437. Final R indices [I > 2r(I)]: R1 =
0
.0442, wR2 = 0.1082, R indices (all data): R1 = 0.0528;
References
wR2 = 0.1121. Its crystal structure has been deposited at
the Cambridge Crystallographic Data Center and has
been allocated the deposition numbers: CCDC 213072.
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1
. (a) Miyashita, A.; Yasuda, H.; Takaya, K.; Toriumi, T.;
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1
2
3
9
T. J. Org. Chem. 1993, 58, 1945; (c) Uozumi, Y.;
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. (a) MOP (X = OMe) was developed by Hayashi. See: Ref.
2
c. (a) MAP (X = NMe ). See: Vyskoil, S.; Smrina, M.;
2
15. (a) Hayashi, T.; Kishi, K.; Yamamoto, A.; Ito, Y.
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X = AsPh , see: Cho, S. Y.; Shibasaki, M. Tetrahedron
6
1
2