Chiral imidazoline-phosphine ligands for palladium-catalyzed asymmetric allylic substitutions

Article abstract of DOI:10.1021/om2008309

Chiral imidazoline-phosphine ligands with a 1,1′-binaphthalene framework have been developed as new types of N,P ligands. The chiral ligand L1 prepared from (R)-(-)-2-(diphenylphosphino)-1,1′-binaphthyl-2′-acid efficiently affects the palladium-catalyzed

Full text of DOI:10.1021/om2008309

Article
pubs.acs.org/Organometallics
Chiral Imidazoline−Phosphine Ligands for Palladium-Catalyzed
Asymmetric Allylic Substitutions
Liang-yong Mei,† Zhi-liang Yuan,† and Min Shi†,*,‡
†Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China
University of Science and Technology, 130 Mei-Long Road, Shanghai 200237, China
‡State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354
Fenglin Road, Shanghai 200032, China
S
* Supporting Information
ABSTRACT: Chiral imidazoline−phosphine ligands with a
1,1′-binaphthalene framework have been developed as new
types of N,P ligands. The chiral ligand L1 prepared from (R)-
(−)-2-(diphenylphosphino)-1,1′-binaphthyl-2′-acid efficiently
affects the palladium-catalyzed enantioselective allylic alkylation
of 1,3-diarylpropenyl acetate with dimethyl malonate to give the
corresponding adducts in excellent yields and enantioselectiv-
ities (up to 96% ee), and chiral ligand L9 can be used for the
palladium-catalyzed asymmetric allylic monofluoromethylation
of 1,3-diphenylpropenyl acetate with 1-fluorobis-
(phenylsulfonyl)methane to afford the corresponding product
in excellent enantioselectivities (up to 98% ee) and moderate
yields under mild conditions. The bidentate N,P-coordination
pattern to the Pd atom with ligand L1 has been unambiguously confirmed by X-ray diffraction.
1,3-diarylpropenyl acetate with dimethyl malonate in the
presence of a base, which has become a versatile process that
is widely used in organic synthesis for the enantioselective
formation of carbon−carbon bonds.7 With regard to the
phosphine−oxazoline ligands LD, these interesting ligands were
initially explored by Hayashi, Uozumi, and their co-workers6b
and have been applied in the palladium-catalyzed asymmetric
allylic alkylation of racemic 1,3-diphenyl-2-propenyl acetate
with the sodium salt of dimethyl malonate, affording the
corresponding product in quantitative yield along with up to
91% ee value. On the other hand, as a structural analogue of 2-
oxazolines,8 chiral 2-imidazolines9 have recently attracted much
attention in asymmetric catalysis and have been utilized as
ligands in various asymmetric transformations. In this case, the
different substitutions on the nitrogen atom can exert diverse
electronic effects in catalytic asymmetric reactions. A typical
example is the interesting Boehringer−Ingelheim phosphinoi-
midazoline (BIPI) ligands developed by Busacca and his co-
workers.10 These ligands have been used to catalyze the
asymmetric Heck reaction to give the desired products in
moderate yields along with moderate ee values. Both of these
findings arouse our interest in the design and synthesis of new
chiral imidazoline−phosphine-type ligands with an axial chiral
1,1′-binaphthalene framework.
INTRODUCTION
■
With the dramatic growth of chiral compounds in the
development of pharmaceuticals, agrochemicals, and materials,
the development of attractive asymmetric methodologies for
producing enantiomerically pure products is of great value. One
of the most important methods to attain chiral substances is
homogeneous enantioselective catalysis with chiral transition
metal complexes derived from transition metals and chiral
ligands, where a small amount of chiral materials can produce a
large amount of chiral products. Chiral ligands such as 2,2′-
bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) (LA)1 pos-
sessing C2 symmetry and 2-(diphenylphosphino)-1,1′-binaphth-
yl (MOP) (LB) (X = OMe)2 possessing C1 symmetry with the
axial chiral 1,1′-binaphthalene framework have attracted much
attention in asymmetric catalysis and have been widely used in
a variety of asymmetric transformations (Figure 1). Thus far,
extensive efforts have been devoted to the design and synthesis
of new binaphthalene-templated ligands. For example, the
binaphthyl P,X-heterodonor ligands LB−LD are representative
examples where X is different heteroatoms (X = NMe2, SMe,
AsPh2, P(O)Ph2, P(S)Ph2, PAr2),3 such as the phosphine−
phosphoramidite ligand LC,4 derived from a phosphane−
phosphite ligand (BINAPHOS),5 and phosphine−oxazoline
ligands LD,6 prepared from (R)-(−)-2-(diphenylphosphino)-
1,1′-binaphthyl-2′-acid (BINDPCA).6 Most of these axial chiral
ligands having bidentate nitrogen and phosphorus donors
(both homo- and heterodonors) have been successfully applied
to the palladium-catalyzed asymmetric allylic substitutions of
Received: September 4, 2011
Published: November 16, 2011
© 2011 American Chemical Society
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Figure 1. Structure of C2-symmetric BINAP and C1-symmetric binaphthyl P,X-heterodonor ligands.
Scheme 1. Preparation of Imidazoline−Phosphine-Type Ligands L1−L10
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Table 1. Screening of Concentration, Solvents, Temperature, and Additives in Asymmetric Allylic Alkylation Reactions
a
b
c
d
entry
solvent
temp [°C]
time [h]
additive
yield [%]
ee [%]
absolute configuration
e
1
THF
rt
rt
rt
rt
rt
rt
0
36
24
24
24
24
24
36
36
24
24
31
96
93
74
74
40
96
31
90
90
96
95
94
95
96
95
96
97
93
R
R
R
R
R
R
R
R
R
2
THF
3
toluene
DCM
DMA
dioxane
THF
4
5
6
7
8
DME
THF
0
9
rt
rt
LiCl
CH3COOK
10
THF
86
R
a
b
c
The reaction was conducted with allyl acetate (0.1 mmol) and malonic ester (0.1 mmol) in solvent (0.5 mL). Isolated yield. The ee values were
d
determined by chiral HPLC on Chiralcel AD. The absolute configuration was determined by comparing the sign of specific rotation with authentic
sample reported in ref 12. The reaction was conducted with allyl acetate (0.1 mmol) and malonic ester (0.1 mmol) in solvent (1.0 mL).
e
Table 2. Catalytic Behavior of Ligands L2−L10 in Asymmetric Allylic Alkylation Reaction
a
b
c
d
entry
ligand
yield [%]
ee [%]
absolute configuration
1
2
3
4
5
6
7
8
9
L2
L3
L4
L5
L6
L7
L8
L9
L10
65
62
86
83
81
90
93
88
90
80
80
95
93
91
95
94
96
96
R
S
S
R
R
R
R
R
R
c
a
b
The reaction was conducted with allyl acetate (0.1 mmol) and malonic ester (0.1 mmol) in solvent (0.5 mL). Isolated yield. The ee values were
determined by chiral HPLC on Chiralcel AD. The absolute configuration was determined by comparing the sign of specific rotation with authentic
d
sample reported in ref 12.
On the basis of the above analysis on combining an axial
chiral 1,1′-binaphthalene framework with 2-imidazoline, we
attempted to explore novel chiral imidazoline−phosphine-type
ligands for asymmetric reactions under mild conditions. In this
paper, we wish to report that chiral ligand L1 prepared from
(R)-(−)-2-(diphenylphosphino)-1,1′-binaphthyl-2′-acid can ef-
ficiently affect the palladium-catalyzed enantioselective allylic
substitution reaction of 1,3-diarylpropenyl acetate with
dimethyl malonate to give the corresponding adducts in
excellent yields and enantioselectivities (up to 96% ee), and
chiral ligand L9 could be used for the palladium-catalyzed
asymmetric allylic monofluoromethylation of 1,3-diphenylpro-
penyl acetate with 1-fluoro-bis(phenylsulfonyl)methane to
afford the corresponding product in excellent enantioselectiv-
ities (up to 98% ee) and moderate to good yields under mild
conditions. The bidentate N,P-coordination pattern to the Pd
center by ligand L1 has been unambiguously confirmed by X-
ray diffraction.
(R)-BINDPCA 1a−1e or 1f, as illustrated in Scheme 1.
Bisphenyl N-tosyl chiral ethylene diamines 2a, bisphenyl N-
mesyl chiral ethylene diamines 2b, and bisphenyl N-nosyl chiral
ethylene diamines 2c were synthesized from the corresponding
(1S,2S)-(−)-1,2-diphenylethylenediamine or (1R,2R)-(+)-1,2-
diphenylethylenediamine. Precursors 3aa−3fc were obtained in
good yields from the condensation of 2 with (R)-BINDPCA
1a−1e or 1f in the presence of 1-ethyl-3-(3-
dimethylaminopropyl)carbodiimide hydrochloride (EDCI)
(1.0 mmol) and 1-hydroxybenzotriazole (1.5 mmol) in N,N-
dimethylformamide (DMF). Then precatalysts 4aa−4ab were
synthesized from 3aa−3ab through imidazoline formation
using the Hendrickson’s reagent,11 while ligand L10 was
obtained directly from 3fc in this way in moderate yield. After
reduction of 4 with HSiCl3 and Et3N in toluene under reflux,
the desired ligands L1−L9 could be obtained in moderate
yields in two steps. Chiral ligand (aR,R,R)-L2 was prepared
from (R)-BINDPCA with (1R,2R)-(+)-1,2-diphenylethylenedi-
amine, and chiral ligands (aS,S,S)-L3 and (aS,R,R)-L4 were
prepared from (S)-BINDPCA with (1S,2S)-(−)-1,2-diphenyle-
thylenediamine and (1R,2R)-(+)-1,2-diphenylethylenediamine,
respectively, under identical conditions (Scheme 1).
RESULTS AND DISCUSSION
■
1. Synthesis of Chiral Ligands L1−L10. Chiral imidazo-
line−phosphine-type ligands L1−L10 were synthesized from
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Scheme 2. Scope of Substrates for Pd/L1-Catalyzed Asymmetric Allylic Alkylations
Table 3. Optimization of the Pd-Catalyzed Enantioselective Allylic Fluorobis(phenylsulfonyl)methylation of Allylic Acetate
a
b
c
d
entry
ligand
solvent
temp [°C]
time [h]
yield [%]
ee [%] (abs. config.)
1
L1
L2
L3
L4
L5
L6
L7
L8
L7
L7
L7
L7
L7
DCM
DCM
DCM
DCM
DCM
DCM
DCM
DCM
DCM
DMF
0
0
36
36
36
36
36
36
36
36
12
12
12
12
12
12
53
63
22
16
30
24
20
73
trace
86
80
78
80 (S)
80 (S)
71 (R)
88 (R)
76 (S)
19 (S)
92 (S)
56 (S)
88 (S)
ND
2
3
0
4
0
5
0
6
0
7
0
8
0
9
rt
rt
rt
rt
rt
10
11
12
13
CH3CN
toluene
THF
95 (S)
97 (S)
84 (S)
a
b
The reaction was conducted with allyl acetate (0.1 mmol) and CHF(SO2Ph)2 (0.11 mmol) in DCM (0.5 mL) at 0 °C for 12 h. Isolated yield.
c
d
The ee values were determined by chiral HPLC on Chiralcel AD. The absolute configuration was determined by comparing the sign of specific
rotation with authentic sample reported in ref 7f.
2. Catalytic Asymmetric Allylic Alkylation of 1,3-
Diphenyl-2-propenyl Acetate in the Presence of
Imidazoline−Phosphine-Type Ligands. Initial examina-
tions using 1,3-diphenylpropenyl acetate 5a and dimethyl
malonate 6a as the model substrates in the presence of chiral
imidazoline−phosphine-type ligand L1 and [Pd(η3-C3H5)Cl]2
were aimed at screening the optimal conditions, and the results
of these experiments are summarized in Table 1. Using
bis(trimethylsilyl)acetamide as an organic base, the yield was
much higher when the concentration of reaction mixtures was
raised from 0.1 to 0.2 M in tetrahydrofuran (THF) at room
temperature (Table 1, entries 1 and 2). By screening different
solvents such as toluene, dichloromethane (DCM), dimethyl
acetamide (DMA), and 1,4-dioxane, we found that THF was
the best one for this asymmetric allylic alkylation, affording the
corresponding product 7aa in 95% ee and 96% yield at room
temperature within 24 h (Table 1, entries 3−6). Upon lowering
the reaction temperature to 0 °C, no evident improvement of
ee and yield could be observed after 36 h (Table 1, entries 7
and 8). The presence of salt additives, such as LiCl or KOAc,
did not improve the ee values in this reaction, and the products
were obtained in relatively lower yields (Table 1, entries 9 and
10). The absolute configuration of the products was assigned as
R by comparison of the optical rotation of the products with
that in the previous literature and their retention time on
HPLC with the literature value.12
Ligands L2−L10 were also examined in the asymmetric
allylic alkylation under the optimized conditions, and the results
are summarized in Table 2. The corresponding products 7aa
were obtained in good to high ee values and moderate to good
yields, and ligand L1 gave the best result (Table 2, entries 1−
9). In addition, as expected, we found that ligands L3 and L4
derived from (S)-BINDPCA produced the corresponding
products with opposite absolute configuration (Table 2, entries
2 and 3).
To illustrate the generality of the high catalytic ability of
ligand L1, other substrates were also tested under optimized
conditions, and the results are shown in Scheme 2. Replacing
dimethyl malonate 6a with diethyl malonate 6b gave the
corresponding adduct 7ab in excellent yield and 94% ee value.
At the same time, using 5b, having a moderately electron-
donating group on the benzene ring, or 5c, having an electron-
withdrawing group on the benzene ring, as the substrate also
gave the corresponding products 7ba and 7ca in high yields and
94% ee values, suggesting that the electronic property of the
substrate did not have a significant impact on the reaction
outcome. Moreover, product 7da was obtained in 83% yield
and up to 96% ee value using 5d as the substrate, which has a
Br atom on the benzene ring. Their absolute configurations
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Table 4. Catalytic Behavior of Ligands L1−L10 in Allylic Fluorobis(phenylsulfonyl)methylation of Allylic Acetate under
Optimized Conditions
a
b
c
d
entry
ligand
yield [%]
ee [%]
absolute configuration
1
2
3
4
5
6
7
8
9
L1
L2
L3
L4
L5
L6
L8
L9
L10
81
75
71
81
75
73
71
81
83
94
74
74
95
88
88
95
98
97
S
S
R
R
S
S
S
S
S
b
a
c
The reaction was conducted with allyl acetate (0.1 mmol) and CHF(SO2Ph)2 (0.11 mmol) in CH3CN (0.5 mL) at rt for 12 h. Isolated yield. The
ee values were determined by chiral HPLC on Chiralcel AD. The absolute configuration was determined by comparing the sign of specific rotation
with authentic sample reported in ref 7f.
d
were also determined to be R by comparison of the optical
rotation of the products and their retention time on HPLC
with the previous literature value.13,14
decided to prepare a Pd(II) complex from L1 with
bis(benzonitrile)palladium dichloride [Pd(PhCN)2Cl2] because
it has been known that nitrogen and phosphorus atoms can
coordinate to the Pd(II) atom to give a stable Pd(II) complex,
which can be confirmed by X-ray diffraction.15 The synthesis of
the Pd(L1)Cl2 complex was carried out by the reaction of
Pd(PhCN)2Cl2 (19 mg, 0.05 mmol) with 1.0 equiv of L1 (41
mg, 0.05 mmol) in CH2Cl2 at room temperature for 1 h under
an argon atmosphere. Degassed hexane (5.0 mL) was then
slowly added, which led to the precipitation of the formed
complex. The mother liquor was filtered off, and the precipitate
was washed with hexane (2 × 1.0 mL) to afford the (R)-
(+)-complex A as a yellow powder (41 mg, 91% yield). Single
crystals suitable for X-ray diffraction were obtained by
recrystallization from chloroform. The ORTEP drawing of
the Pd(L1)Cl2 complex is shown in Figure 2, and the
corresponding CIF data are presented in the Supporting
Information.16 From Figure 2, it can be seen that L1 acts as a
cis-bidentate ligand to the Pd(II) center in a slightly distorted
planar geometry with both nitrogen and phosphorus atoms
providing an eight-membered chelate ring. The angle of the
N(1)−Pd(1)−P(1) plane is 92.65°, and the bond lengths of
N(1)−Pd(1) and Pd(1)−P(1) are 2.051 and 2.2416 Å,
respectively.
To gain more detailed information on the difference of our
imidazoline−phosphine ligands with phosphine−oxazoline
ligands LD, the comparison of structures between our Pd
complex with the Pd(LD)Cl2 (Y = iPr) complex6g has been
carried out. We found that the Pd−P and Pd−N bond lengths
as well as the N−Pd−P bond angles are very similar in the two
Pd complexes, and the main difference lies in the different
substitution on the nitrogen atom in our imidazoline−
phosphine ligand system, which can exert different electronic
effects in catalytic asymmetric reactions. A typical example is
that in the Pd-catalyzed asymmetric allylic monofluoromethy-
lation, we found that replacing Ts with Ms or Ns on the
nitrogen atom gave the corresponding product in higher ee
value (Table 4, entries 1, 8, 9). On the other hand, as for these
asymmetric allylic substitutions, our imidazoline−phosphine
ligands gave relatively better yields and ee values even under
3. Catalytic Asymmetric Allylic Monofluoromethyla-
tion of 1,3-Diphenyl-2-propenyl Acetate in the Presence
of Imidazoline−Phosphine-Type Ligands. Initial exami-
nations of allylic monofluoromethylation of 1,3-diphenylpro-
penyl acetate 5a with 1-fluoro-bis(phenylsulfonyl)methane
were examined in DCM using L1−L8 as the chiral ligands in
the presence of cesium carbonate at 0 °C,7f and the results of
these experiments are summarized in Table 3. However, we
found that the yields of the corresponding product 8 were
rather low even though the ee values were moderate to good
after 36 h, and using L7 as the chiral ligand afforded the
corresponding product 8 in 24% yield and 94% ee (Table 3,
entries 1−8). By conducting the experiment at room
temperature using L7 as the ligand, product 8 was obtained
in 73% yield and 88% ee (Table 4, entry 9). By screening
different solvents at room temperature using L7 as the ligand,
we found that CH3CN was the solvent of choice for this
asymmetric allylic monofluoromethylation, affording the
corresponding product 8 in 95% ee and 86% yield at room
temperature (Table 4, entries 10−13). The absolute config-
uration of the product was determined to be S by comparison
of the optical rotation of the product and its retention time on
HPLC with the literature data (Table 4, entry 11).7f
Ligands L1−L6 and L8−L10 were also tested in the
asymmetric allylic monofluoromethylation under the optimized
conditions, and the results are summarized in Table 4. The
corresponding product 8 was obtained in 71−83% yields and
74−98% ee values (Table 4, entries 1−9). As for L9 and L10,
the corresponding product was obtained in moderate yield and
up to 98% ee value, presumably due to the electronic effect
caused by the different substitution on the nitrogen atom
(Table 4, entries 8 and 9). In addition, as expected, ligands L3
and L4 derived from (S)-BINDPCA produced the correspond-
ing product 8 with opposite absolute configuration (Table 4,
entries 3 and 4).
4. Synthesis of Pd(L1)Cl2 Complex A. In order to get
direct evidence of N,P-coordination to the Pd center, we
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the major enantiomer was assigned according to the sign of the specific
rotation. In addition, chiral 2-(diphenylphosphino)-1,1′-binaphthyl-2′-
acids (BINDPCA) were synthesized from the corresponding (R)-
(+)-1,1′-bi-2-naphthol and (S)-(−)-1,1′-bi-2-naphthol, respectively
(for more detailed information, please see ref 6).
Typical Procedure of the Preparation of Chiral Imidazoline-
Phosphine-Type Ligands L1−L10. Synthesis of the Precatalysts
3. A solution of (R)-BINDPCA 1a−1e or 1f (0.5 mmol) in DMF (5.0
mL) with 1-ethyl-3-(3-dimethyllaminopropyl)carbodiimide hydro-
chloride (EDCI) (1.0 mmol) and 1-hydroxybenzotriazole (1.5
mmol) was stirred at 0 °C for 10 min. Then a solution of 2 (0.75
mmol) in 2.0 mL of DMF was added into the solution by syringe at 0
°C. The reaction mixture was stirred at room temperature for 5 h. The
reaction mixture was diluted by the addition of 10 mL of EtOAc, then
washed with H2O and brine, and dried over anhydrous Na2SO4. The
solvent was removed under vacuum, and the residue was purified by
silica gel column chromatography (PE/EA = 1.5:1) to give the desired
product 3 as a pale yellow solid.
(R)-2-(Diphenylphosphoryl)-N-((1S,2S)-2-(4-methylphenylsulfo-
namido)-1,2-diphenylethyl)-1,1′-binaphthyl-2-carboxamide, 3aa.
Yield: 392 mg, 93%; pale yellow solid, mp 133−136 °C; IR (CH2Cl2)
ν 3209, 3059, 2924, 1659, 1566, 1497, 1453, 1439, 1373, 1332, 1262,
Figure 2. ORTEP drawing of Pd(L1)Cl2 complex A with thermal
ellipsoids at the 30% probability level. Selected bond distances (Å) and
angles (deg): Pd1−P1 = 2.2416(7), Pd1−N1 = 2.051(2), N1−C21 =
1.272(3), Cl1−Pd1 = 2.2920(6), Cl2−Pd1 = 2.3447(7), N1−Pd1−P1
= 92.65(6), C1−P1−Pd1 = 117.72(8), N1−Pd1−Cl2 = 91.53(6),
Cl1−Pd1−Cl2 = 89.43(2), Cl1−Pd1−P1 = 86.65(2), C11−C20−C21
= 117.5(2).
1
1202, 1158, 1114, 1090, 1071, 1029, 1000, 972, 952 cm−1; H NMR
(CDCl3, TMS, 300 MHz) δ 2.24 (s, 3H, CH3), 5.04 (dd, 1H, J1 = 3.6
Hz, J2 = 9.6 Hz, CH), 5.27 (dd, 1H, J1 = 3.6 Hz, J2 = 8.7 Hz, CH), 6.04
(br, 2H, ArH), 6.36 (d, 2H, J = 7.8 Hz, ArH), 6.45 (d, 1H, J = 8.4 Hz,
ArH), 6.76−6.86 (m, 5H, ArH), 6.94−6.99 (m, 2H, ArH), 7.09−7.22
(m, 7H, ArH), 7.24−7.33 (m, 4H, ArH), 7.44−7.50 (m, 4H, ArH),
7.57 (t, 4H, J = 5.4 Hz, ArH), 7.76−7.83 (m, 3H, ArH), 7.88 (d, 1H, J
= 8.1 Hz, ArH), 7.98 (d, 1H, J = 6.9 Hz, ArH), 10.29 (d, 1H, J = 8.7
Hz, NH); 31P NMR (CDCl3, 121 MHz, 85% H3PO4) δ 31.92; MS
(ESI) m/z (%) 847.7 (100) [M+ + 1]; HRMS (MALDI) calcd for
milder conditions as compared with phosphine−oxazoline
ligands LD reported before.6b,f
In summary, a series of novel chiral imidazoline−phosphine
ligands L1−L10 has been successfully synthesized and used for
the Pd-catalyzed allylic substitution reactions. Ligand L1,
prepared from (R)-2-(diphenylphosphino)-1,1′-binaphthyl-2′-
acid (BINDPCA), was found to be a very effective chiral ligand
for Pd-catalyzed asymmetric allylic alkylation to give the
corresponding products in excellent enantioselectivities (up to
96% ee) and good yields under mild conditions, while ligand
L9 could be used as an effective chiral ligand for Pd-catalyzed
asymmetric allylic monofluoromethylation to give the corre-
sponding products in excellent enantioselectivities (up to 98%
ee) and moderate yields under mild conditions. Its bidentate
coordination pattern to a Pd metal center with both P and N
atoms has been unambiguously established by X-ray diffraction.
Efforts to use these novel chiral imidazoline−phosphine-type
ligands for other asymmetric reactions are under way.
C54H44N2O4PS+1(M+ + 1) requires 847.2755, found 847.2753. [α]20
D
= +108.6 (c 0.40, CHCl3).
(R)-2-(Bis(3,5-dimethylphenyl)phosphoryl)-N-((1S,2S)-2-((4-meth-
ylphenylsulfonamido)-1,2-diphenylethyl)-1,1′-binaphthyl-2-carbox-
amide, 3ba. Yield: 297 mg, 78%; pale yellow solid, mp 130−133 °C;
IR (CH2Cl2) ν 3201, 3059, 3031, 2922, 1725, 1660, 1620, 1566, 1498,
1452, 1422, 1375, 1334, 1305, 1272, 1224, 1203, 1159, 1122, 1092,
1065, 1007, 973, 953 cm−1; 1H NMR (CDCl3, TMS, 300 MHz) δ 1.97
(s, 6H, CH3), 2.25 (s, 3H, CH3), 2.40 (s, 6H, CH3), 4.97 (dd, 1H, J1 =
3.6 Hz, J2 = 10.2 Hz, CH), 5.28 (dd, 1H, J1 = 3.6 Hz, J2 = 9.3 Hz, CH),
6.23 (d, 2H, J = 7.8 Hz, ArH), 6.47 (s, 1H, ArH), 6.57 (d, 1H, J = 8.4
Hz, ArH), 6.70−6.84 (m, 5H, ArH), 6.88−6.91 (m, 1H, ArH), 6.97−
7.02 (m, 2H, ArH), 7.04−7.26 (m, 9H, ArH), 7.45−7.49 (m, 4H,
ArH), 7.58−7.73 (m, 4H, ArH), 7.90 (d, 1H, J = 8.4 Hz, ArH), 8.05
(dd, 1H, J1 = 2.1 Hz, J2 = 8.4 Hz, ArH), 8.22 (d, 1H, J = 10.2 Hz,
ArH), 10.28 (d, 1H, J = 9.3 Hz, NH); 31P NMR (CDCl3, 121 MHz,
85% H3PO4) δ 30.39; MS (ESI) m/z (%) 903.7 (100) [M+ + 1];
HRMS (MALDI) calcd for C58H52N2O4PS+ (M+ + 1) requires
903.3388, found 903.3380. [α]20 = +48.0 (c 0.15, CHCl3).
EXPERIMENTAL SECTION
D
■
(R)-2-(Bis(3,5-dimethoxyphenyl)phosphoryl)-N-((1S,2S)-2-((4-
methylphenylsulfonamido)-1,2-diphenylethyl)-1,1′-binaphthyl-2-
carboxamide, 3ca. Yield: 319 mg, 75%; pale yellow solid, mp 137−
139 °C; IR (CH2Cl2) ν 3210, 3060, 3002, 2933, 2838, 1723, 1660,
1585, 1498, 1453, 1419, 1373, 1335, 1303, 1289, 1257, 1206, 1161,
1091, 1063, 973, 953, 925 cm−1; 1H NMR (CDCl3, TMS, 300 MHz) δ
2.23 (s, 3H, CH3), 3.56 (s, 6H, OCH3), 3.77 (s, 6H, OCH3), 4.99 (dd,
1H, J1 = 3.0 Hz, J2 = 9.9 Hz, CH), 5.31 (dd, 1H, J1 = 3.0 Hz, J2 = 9.0
Hz, CH), 5.89 (s, 1H, ArH), 6.25 (d, 4H, J = 6.9 Hz, ArH), 6.54 (d,
1H, J = 8.1 Hz, ArH), 6.67 (s, 1H, ArH), 6.74−6.82 (m, 4H, ArH),
6.89−7.04 (m, 3H, ArH), 7.11−7.20 (m, 9H, ArH), 7.38−7.47 (m,
3H, ArH), 7.54 (d, 1H, J = 8.1 Hz, ArH), 7.65−7.75 (m, 2H, ArH),
7.88 (d, 1H, J = 8.4 Hz, ArH), 7.97−8.06 (m, 2H, ArH), 10.13 (d, 1H,
J = 9.0 Hz, NH); 31P NMR (CDCl3, 121 MHz, 85% H3PO4) δ 31.98;
MS (ESI) m/z (%) 967.9 (100) [M+ + 1]; HRMS (MALDI) calcd for
General Methods. Melting points were obtained with a
Yanagimoto micro melting point apparatus and are uncorrected.
Optical rotations were determined in a solution of CHCl3 or CH2Cl2
at 20 °C by using a Perkin-Elmer-241 MC polarimeter; [α]D values are
given in units of 10−1 deg cm2 g−1. Infrared spectra were measured on
a spectrometer. 1H NMR spectra were recorded for solutions in
CDCl3 with tetramethylsilane (TMS) as internal standard; 31P NMR
spectra were recorded for a solution in CDCl3 with 85% H3PO4 as the
external reference. J-values are in Hz. Mass spectra were recorded with
a HP-5989 instrument, and HRMS was measured by a Finnigan MA+
mass spectrometer. Organic solvents used were dried by standard
methods when necessary. Commercially obtained reagents were used
without further purification. All reactions were monitored by TLC
with Huanghai GF254 silica gel coated plates. Flash column
chromatography was carried out using 300−400 mesh silica gel at
increased pressure. All reactions were performed under argon using
standard Schlenk techniques. The optical purities of products were
determined by HPLC analysis using a chiral stationary phase column
(column, Daicel Co. Chiralcel AD), and the absolute configuration of
C58H52N2O8PS+ (M+ + 1) requires 967.3192, found 967.3177. [α]20
D
= +58.3 (c 0.40, CHCl3).
(R)-2-((4-Fluorophenyl)phosphoryl)-N-((1S,2S)-2-(4-methylphe-
nylsulfonamido)-1,2-diphenylethyl)-1,1′-binaphthyl-2-carboxa-
mide, 3da. Yield: 428 mg, 97%; pale yellow solid, mp 168−170 °C;
6471
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Article
IR (CH2Cl2) ν 3206, 3060, 1657, 1592, 1498, 1399, 1331, 1304, 1265,
CH2Cl2. The combined organic phase was dried over anhydrous
Na2SO4, and the solvent was removed under vacuum. The residue was
purified by silica gel column chromatography (PE/EA = 1:1) to give
crude product 4 (mixed with triphenylphosphine oxide) or ligand L10.
(4S,5S)-2-((R)-2′-(diphenylphosphino)-1,1′-binaphthyl-2-yl)-4,5-
diphenyl-1-nosyl-4,5-dihydro-1H-imidazoline, L10. Yield: 160 mg,
52%; pale yellow solid, mp 151−154 °C; IR (CH2Cl2) ν 3165, 3060,
2915, 1661, 1567, 1529, 1439, 1348, 1311, 1263, 1165, 1113, 1190,
1233, 1159, 1114, 1090, 1071, 1013, 973, 953, 908, 873, 825, 736, 700,
1
677, 650 cm−1; H NMR (CDCl3, TMS, 300 MHz) δ 2.25 (s, 3H,
CH3), 5.02 (dd, 1H, J1 = 3.9 Hz, J2 = 9.6 Hz, CH), 5.25 (dd, 1H, J1 =
3.9 Hz, J2 = 8.7 Hz, CH), 6.36 (d, 2H, J = 7.5 Hz, ArH), 6.40−6.49
(m, 3H, ArH), 6.82−6.87 (m, 5H, ArH), 6.98 (t, 1H, J = 7.5 Hz, ArH),
7.09−7.23 (m, 12H, ArH), 7.29−7.31 (m, 2H, ArH), 7.36−7.44 (m,
1H, ArH), 7.49 (t, 1H, J = 7.5 Hz, ArH), 7.57 (d, 1H, J = 8.1 Hz,
ArH), 7.64−7.78 (m, 4H, ArH), 7.90 (d, 1H, J = 8.1 Hz, ArH), 7.99
(dd, 1H, J1 = 1.8 Hz, J2 = 8.4 Hz, ArH), 9.99 (d, 1H, J = 8.7 Hz, NH);
31P NMR (CDCl3, 121 MHz, 85% H3PO4) δ 30.76; 19F NMR
(CDCl3, 282 MHz, CFCl3) δ −105.97, −107.67; MS (ESI) m/z (%)
883.7 (100) [M+ + 1]; HRMS (ESI) calcd for C54H42N2O4F2PS+ (M+
1
847, 736, 700, 540, 525 cm−1; H NMR (CDCl3, TMS, 300 MHz) δ
4.59 (d, 1H, J = 6.0 Hz, CH), 4.66 (d, 1H, J = 6.0 Hz, CH), 5.88 (d,
2H, J = 6.3 Hz, ArH), 6.69 (d, 1H, J = 8.7 Hz, ArH), 6.86 (dd, 5H, J1 =
6.6 Hz, J2 = 13.2 Hz, ArH), 7.01−7.04 (m, 7H, ArH), 7.09−7.25 (m,
8H, ArH), 7.30−7.40 (m, 3H, ArH), 7.54−7.60 (m, 2H, ArH), 7.67
(d, 1H, J = 8.7 Hz, ArH), 7.74 (d, 2H, J = 8.4 Hz, ArH), 7.93−7.99
(m, 2H, ArH), 8.06 (dd, 2H, J1 = 3.0 Hz, J2 = 8.4 Hz, ArH), 8.18 (d,
1H, J = 8.7 Hz, ArH); 31P NMR (CDCl3, 121 MHz, 85% H3PO4) δ
−14.33; MS (MALDI) m/z (%): 844.5 (100) [M+ + 1]; HRMS
(MALDI) calcd for C53H39N3O4PS+ (M+ + 1) requires 844.2409,
+ 1) requires 883.2560, found 883.2566. [α]20 = +104.2 (c 0.90,
D
CHCl3).
(R)-2-((4-Methylphenyl)phosphoryl)-N-((1S,2S)-2-(4-methylphe-
nylsulfonamido)-1,2-diphenylethyl)-1,1′-binaphthyl-2-carboxa-
mide, 3ea. Yield: 332 mg, 76%; pale yellow solid, mp 178−180 °C;
IR (CH2Cl2) ν 3193, 3030, 2245, 1917, 1656, 1600, 1559, 1497, 1451,
1399, 1330, 1156, 1113, 1089, 1065, 1020, 971, 952, 911, 872, 851,
811, 762, 698, 676, 662, 648, 618 cm−1; 1H NMR (CDCl3, TMS, 300
MHz) δ 2.01 (s, 3H, CH3), 2.23 (s, 3H, CH3), 2.39 (s, 3H, CH3), 5.02
(dd, 1H, J1 = 3.9 Hz, J2 = 9.9 Hz, CH), 5.28 (dd, 1H, J1 = 3.9 Hz, J2 =
9.9 Hz, CH), 6.33 (d, 2H, J = 7.2 Hz, ArH), 6.44−6.52 (m, 3H, ArH),
6.78−6.85 (m, 5H, ArH), 6.95−7.07 (m, 4H, ArH), 7.14−7.21 (m,
7H, ArH), 7.27−7.31 (m, 2H, ArH), 7.39−7.55 (m, 5H, ArH), 7.62
(d, 1H, J = 8.7 Hz, ArH), 7.76 (dd, 1H, J1 = 8.1 Hz, J2= 11.4 Hz, ArH),
7.86 (d, 1H, J = 8.1 Hz, ArH), 7.95−8.01 (m, 1H, ArH), 10.22 (d, 1H,
J = 9.3 Hz, NH); 31P NMR (CDCl3, 121 MHz, 85% H3PO4) δ 31.72;
MS (ESI) m/z (%) 875.7 (100) [M+ + 1]; HRMS (ESI) calcd for
found 844.2393. [α]20 = +57.0 (c 2.00 CHCl3).
D
Synthesis of the Chiral Imidazoline−Phosphine Ligands L1−L9.
To a dried Schlenk tube filled with argon was added crude precatalyst
4 with Et3N (10.0 equiv) in 15 mL of anhydrous toluene. The mixture
was stirred at 0 °C for 10 min, 10.0 equiv of HSiCl3 was added at 0 °C,
and the mixture was stirred at that temperature for 0.5 h. Then the
mixture was allowed to warm to room temperature and stirred under
reflux overnight. After cooling to room temperature, the reaction was
quenched with saturated NaHCO3(aq), the precipitates settled out,
and the aqueous layer was extracted with EtOAc. The combined
organic phase was washed with brine and dried over anhydrous
Na2SO4, and the solvent was removed under vacuum. The residue was
purified by silica gel column chromatography (PE/EA = 5:1) to give
the desired product as a pale yellow solid.
C56H48N2O4PS+ (M+ + 1) requires 875.3085, found 875.3067. [α]20
D
= +90.7 (c 0.90, CHCl3).
(R)-2-(Diphenylphosphoryl)-N-((1S,2S)-2-(methylsulfonamido)-
1,2-diphenylethyl)-1,1′-binaphthyl-2-carboxamide, 3ab. Yield: 316
mg, 82%; pale yellow solid, mp 143−145 °C; IR (CH2Cl2) ν 3202,
3058, 1659, 1567, 1438, 1326, 1148, 1119, 1092, 983, 818, 749, 723,
(4S,5S)-2-((R)-2′-(Diphenylphosphino)-1,1′-binaphthyl-2-yl)-4,5-
diphenyl-1-tosyl-4,5-dihydro-1H-imidazoline, L1. Yield: 110 mg,
55% for two steps; pale yellow solid, mp 150−153 °C; IR (CH2Cl2)
ν 3397, 3055, 2973, 2925, 1725, 1642, 1595, 1479, 1433, 1371, 1306,
1
699, 540, 524, 515 cm−1; H NMR (CDCl3, TMS, 300 MHz) δ 2.13
1277, 1247, 1205, 1185, 1167, 1089, 1026, 963 cm−1 1H NMR
;
(s, 3H, CH3), 5.07 (dd, 1H, J1 = 3.6 Hz, J2 = 9.9 Hz, CH), 5.46 (dd,
1H, J1 = 3.6 Hz, J2 = 8.7 Hz, CH), 6.42 (d, 2H, J = 8.1 Hz, ArH), 6.52
(d, 1H, J = 8.1 Hz, ArH), 6.69 (dt, 2H, J1 = 2.7 Hz, J2 = 7.5 Hz, ArH),
6.89 (t, 4H, J = 7.5 Hz, ArH), 6.96−6.99 (m, 1H, ArH), 7.06−7.18 (m,
5H, ArH), 7.33−7.50 (m, 8H, ArH), 7.56−7.68 (m, 5H, ArH), 7.83−
7.90 (m, 4H, ArH), 8.02 (d, 1H, J = 9.9 Hz, NH), 10.17 (d, 1H, J = 8.7
Hz, NH); 31P NMR (CDCl3, 121 MHz, 85% H3PO4) δ 31.42; MS
(MALDI) m/z (%) 771.3 (100) [M+ + 1]; HRMS (MALDI) calcd for
(CDCl3, TMS, 300 MHz) δ 2.25 (s, 3H, CH3), 4.49 (d, 1H, J = 6.0
Hz, CH), 4.54 (d, 1H, J = 6.0 Hz, CH), 5.84 (d, 2H, J = 7.8 Hz, ArH),
6.68 (d, 1H, J = 8.7 Hz, ArH), 6.77−6.92 (m, 9H, ArH), 6.95−7.04
(m, 5H, ArH), 7.07−7.13 (m, 4H, ArH), 7.16−7.22 (m, 5H, ArH),
7.33 (q, 2H, J = 6.9 Hz, ArH), 7.50−7.57 (m, 2H, ArH), 7.81 (d, 1H, J
= 8.4 Hz, ArH), 7.91 (d, 1H, J = 7.8 Hz, ArH), 7.98−8.04 (m, 3H,
ArH), 8.16 (d, 1H, J = 8.4 Hz, ArH); 31P NMR (CDCl3, 121 MHz,
85% H3PO4) δ −13.79; MS (ESI) m/z (%) 813.6 (100) [M+ + 1];
HRMS (MALDI) calcd for C54H42N2O2PS+ (M+ + 1) requires
C48H40N2O4PS+ (M+ + 1) requires 771.2441, found 771.2441. [α]20
D
= +79.1 (c 0.70, CHCl3).
817.2702, found 817.2699. [α]20 = +36.5 (c 0.45, CHCl3).
D
(R)-2-((4-Methylphenylphosphino)-N-((1S,2S)-2-(4-nitrophenyl-
sulfonamido)-1,2-diphenylethyl)-1,1′-binaphthyl-2-carboxamide,
3fc. Yield: 323 mg, 75%; pale yellow solid, mp 139−141 °C; IR
(CH2Cl2) ν 3388, 3058, 2956, 2925, 2855, 1633, 1529, 1496, 1348,
(4R,5R)-2-((R)-2′-(diphenylphosphino)-1,1′-binaphthyl-2-yl)-4,5-
diphenyl-1-tosyl-4,5-dihydro-1H-imidazoline, L2. Yield: 199 mg,
63% for two steps; pale yellow solid, mp 147−150 °C; IR (CH2Cl2)
ν 3401, 3055, 2970, 2925, 1725, 1655, 1590, 1479, 1433, 1389, 1306,
1
1311, 1265, 1166, 1091, 937, 854, 737, 518 cm−1; H NMR (CDCl3,
1271, 1239, 1198, 1185, 1165, 1089, 1026, 969 cm−1 1H NMR
;
TMS, 300 MHz) δ 4.51 (dd, 1H, J1 = 5.1 Hz, J2 = 10.5 Hz, CH), 4.64
(dd, 1H, J1 = 7.2 Hz, J2 = 10.5 Hz, CH), 5.87 (d, 2H, J = 8.1 Hz, ArH),
6.10 (d, 1H, J = 6.3 Hz, ArH), 6.63 (d, 2H, J = 8.1 Hz, ArH), 6.68−
6.90 (m, 7H, ArH), 6.97−7.05 (m, 3H, ArH), 7.09−7.24 (m, 5H,
ArH), 7.28−7.37 (m, 6H, ArH), 7.48−7.51 (m, 4H, ArH), 7.55−7.64
(m, 3H, ArH), 7.87−7.93 (m, 3H, ArH), 8.14 (d, 1H, J = 9.0 Hz, NH),
8.30 (d, 1H, J = 8.1 Hz, NH); 31P NMR (CDCl3, 121 MHz, 85%
H3PO4) δ −14.34; MS (MALDI) m/z (%) 862.5 (100) [M+ + 1];
HRMS (MALDI) calcd for C53H41N3O5PS+ (M+ + 1) requires
(CDCl3, TMS, 300 MHz) δ 2.18 (s, 3H, CH3), 4.48 (d, 1H, J = 4.2
Hz, CH), 4.94 (d, 1H, J = 4.2 Hz, CH), 5.97 (d, 2H, J = 7.5 Hz, ArH),
6.61−6.72 (m, 4H, ArH), 6.79−6.87 (m, 4H, ArH), 6.95−7.05 (m,
10H, ArH), 7.14−7.25 (m, 4H, ArH), 7.28−7.40 (m, 5H, ArH), 7.48
(dd, 1H, J1 = 2.7 Hz, J2 = 8.4 Hz, ArH), 7.58 (d, 1H, J = 7.2 Hz, ArH),
7.70 (d, 1H, J = 8.7 Hz, ArH), 7.91 (d, 1H, J = 8.4 Hz, ArH), 8.01−
8.08 (m, 3H, ArH); 31P NMR (CDCl3, 121 MHz, 85% H3PO4) δ
−11.64; MS (ESI) m/z (%) 813.6 (100) [M+ + 1]; HRMS (MALDI)
calcd for C54H42N2O2PS+ (M+ + 1) requires 817.2702, found:
862.2475, found 862.2499. [α]20 = +38.3 (c 2.00, CHCl3).
817.2698. [α]20 = −19.5 (c 0.35, CHCl3).
D
D
Synthesis of the Precatalysts 4 and Ligand L10 (ref 11). To a
dried Schlenk tube were added triphenylphosphine oxide (1.5 mmol)
and trifluoromethanesulfonic anhydride (1.5 mmol) in CH2Cl2 (5.0
mL) at 0 °C, and the reaction mixture was stirred at 0 °C for 0.5 h.
Then the solution of precatalyst 3 (0.50 mmol) in CH2Cl2 (5.0 mL)
was added slowly via syringe. After the completion of the addition, the
mixture was stirred at 0 °C for 3 h. The reaction was quenched with
saturated NaHCO3(aq), and the aqueous layer was extracted with
(4S,5S)-2-((S)-2′-(Diphenylphosphino)-1,1′-binaphthyl-2-yl)-4,5-
diphenyl-1-tosyl-4,5-dihydro-1H-imidazoline, L3. Yield: 237 mg,
49% for two steps; pale yellow solid, mp 151−153 °C; IR (CH2Cl2)
ν 3358, 3075, 2900, 1755, 1642, 1602, 1598, 1459, 1430, 1361, 1300,
1277, 1247, 1215, 1195, 1165, 1089, 1007, 960 cm−1 1H NMR
;
(CDCl3, TMS, 300 MHz) δ 2.19 (s, 3H, CH3), 4.48 (d, 1H, J = 4.2
Hz, CH), 4.94 (d, 1H, J = 4.2 Hz, CH), 5.97 (d, 2H, J = 7.8 Hz, ArH),
6.62−6.75 (m, 4H, ArH), 6.80−6.87 (m, 4H, ArH), 6.95−7.08 (m,
6472
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10H, ArH), 7.15−7.25 (m, 3H, ArH), 7.28−7.40 (m, 5H, ArH), 7.48
(dd, J1 = 3.0 Hz, J2 = 8.4 Hz 1H, ArH), 7.58 (t, 1H, J = 7.2 Hz, ArH),
7.70 (d, 1H, J = 7.8 Hz, ArH), 7.92 (d, 2H, J = 8.4 Hz, ArH), 8.01−
8.08 (m, 3H, ArH); 31P NMR (CDCl3, 121 MHz, 85% H3PO4) δ
−11.65; MS (ESI) m/z (%) 813.6 (100) [M+ + 1]; HRMS (MALDI)
calcd for C54H42N2O2PS+ (M+ + 1) requires 817.2702, found
−114.30; MS (ESI) m/z (%) 849.6 (100) [M+ + 1]; HRMS (ESI)
calcd for C54H40N2O2F2PS+ (M+ + 1) requires 849.2504, found
849.2511. [α]20 = +44.1 (c 0.55, CHCl3).
D
(4S,5S)-2-((R)-2′-(Bis(4-methylphenyl)phosphino)-1,1′-binaphth-
yl-2-yl)-4,5-diphenyl-1-tosyl-4,5-dihydro-1H-imidazoline, L8. Yield:
153 mg, 48% for two steps; pale yellow solid, mp 150−152 °C; IR
(CH2Cl2) ν 3051, 2920, 2855, 2304, 1913, 1641, 1598, 1495, 1454,
1370, 1339, 1307, 1265, 1186, 1170, 1088, 1057, 1020, 963, 869, 808,
817.2698. [α]20 = +16.8 (c 0.45, CHCl3).
D
(4R,5R)-2-((S)-2′-(Diphenylphosphino)-1,1′-binaphthyl-2-yl)-4,5-
diphenyl-1-tosyl-4,5-dihydro-1H-imidazoline, L4. Yield: 186 mg,
59% for two steps; pale yellow solid, mp 155−158 °C; IR (CH2Cl2)
ν 3411, 3380, 3055, 3020, 2973, 2925, 1725, 1642, 1608, 1479, 1433,
1
775, 736, 698, 667, 627, 610 cm−1; H NMR (CDCl3, TMS, 300
MHz) δ 2.20 (s, 3H, CH3), 2.21 (s, 3H, CH3), 2.25 (s, 3H, CH3), 4.49
(d, 1H, J = 2.7 Hz, CH), 4.52 (d, 1H, J = 2.7 Hz, CH), 5.83 (d, 2H, J =
7.8 Hz, ArH), 6.68−6.91 (m, 14H, ArH), 7.01 (t, 3H, J = 7.5 Hz,
ArH), 7.14−7.23 (m, 5H, ArH), 7.29−7.37 (m, 2H, ArH), 7.49−7.55
(m, 2H, ArH), 7.79 (d, 1H, J = 8.7 Hz, ArH), 7.91 (d, 1H, J = 8.7 Hz,
1371, 1300, 1277, 1247, 1205, 1175, 1157, 1089, 1026, 960, 895 cm−1
;
1H NMR (CDCl3, TMS, 300 MHz) δ 2.28 (s, 3H, CH3), 4.49 (d, 1H,
J = 5.7 Hz, CH), 4.54 (d, 1H, J = 5.7 Hz, CH), 5.85 (d, 2H, J = 7.5 Hz,
ArH), 6.68 (d, 1H, J = 8.4 Hz, ArH), 6.78−6.94 (m, 9H, ArH), 6.96−
7.02 (m, 5H, ArH), 7.07−7.12 (m, 4H, ArH), 7.19 (d, 5H, J = 8.1 Hz,
ArH), 7.31−7.38 (m, 2H, ArH), 7.49−7.58 (m, 2H, ArH), 7.80 (d,
1H, J = 8.1 Hz, ArH), 7.93 (d, 1H, J = 8.1 Hz, ArH), 7.97−8.05 (m,
3H, ArH), 8.17 (d, 1H, J = 8.4 Hz, ArH); 31P NMR (CDCl3, 121
MHz, 85% H3PO4) δ −13.81; MS (ESI) m/z (%) 813.6 (100) [M+ +
1]; HRMS (MALDI) calcd for C54H42N2O2PS+ (M+ + 1) requires
ArH), 8.00 (t, 3H, J = 8.1 Hz, ArH), 8.15 (d, 1H, J = 8.1 Hz, ArH); 31
P
NMR (CDCl3, 121 MHz, 85% H3PO4) δ −15.42; MS (ESI) m/z (%)
841.6 (100) [M+ + 1]; HRMS (ESI) calcd for C56H46N2O2PS+ (M+ +
1) requires 841.2992, found 841.3012. [α]20D = +11.3 (c 0.40, CHCl3).
(4S,5S)-2-((R)-2′-(Diphenylphosphino)-1,1′-binaphthyl-2-yl)-4,5-
diphenyl-1-mesyl-4,5-dihydro-1H-imidazoline, L9. Yield: 130 mg,
42% for two steps; pale yellow solid, mp 146−149 °C; IR (CH2Cl2) ν
3271, 3043, 2915, 2846, 2346, 1668, 1652, 1634, 1489, 1456, 1434,
817.2702, found 817.2700. [α]20 = −36.1 (c 0.40, CHCl3).
D
1
1311, 1151, 1051, 1058, 972, 821, 695, 515, 490 cm−1; H NMR
(4S,5S)-2-((R)-2′-(Bis(3,5-dimethylphenyl)phosphino)-1,1′-bi-
naphthyl-2-yl)-4,5-diphenyl-1-tosyl-4,5-dihydro-1H-imidazoline,
L5. Yield: 138 mg, 50% for two steps; pale yellow solid, mp 150−153
°C; IR (CH2Cl2) ν 3395, 3152, 2958, 2925, 1886, 1725, 1642, 1590,
1485, 1433, 1371, 1316, 1277, 1207, 1185, 1167, 1075, 1029, 1001,
(CDCl3, TMS, 300 MHz) δ 1.76 (s, 3H, CH3), 4.56 (d, 1H, J = 6.6
Hz, CH), 4.94 (d, 1H, J = 6.6 Hz, CH), 6.19 (d, 2H, J = 7.8 Hz, ArH),
6.64 (d, 1H, J = 8.7 Hz, ArH), 6.78 (t, 1H, J = 7.8 Hz, ArH), 6.87 (t,
2H, J = 7.5 Hz, ArH), 6.98−7.06 (m, 5H, ArH), 7.08−7.13 (m, 3H,
ArH), 7.15−7.24 (m, 6H, ArH), 7.29−7.37 (m, 4H, ArH), 7.46 (t, 1H,
J = 7.5 Hz, ArH), 7.56−7.64 (m, 2H, ArH), 7.88−8.01 (m, 3H, ArH),
8.09 (dd, 2H, J1 = 3.6 Hz, J2 = 8.7 Hz, ArH); 31P NMR (CDCl3, 121
MHz, 85% H3PO4) δ −14.28; MS (MALDI) m/z (%) 737.5 (100)
[M++1]; HRMS (MALDI) calcd for C48H38N2O2PS+ (M+ + 1)
1
903 cm−1; H NMR (CDCl3, TMS, 300 MHz) δ 1.88 (s, 6H, CH3),
2.02 (s, 6H, CH3), 2.26 (s, 3H, CH3), 4.47 (d, 1H, J = 5.7 Hz, CH),
4.49 (d, 1H, J = 5.7 Hz, CH), 5.84 (d, 2H, J = 7.8 Hz, ArH), 6.43 (d,
2H, J = 7.8 Hz, ArH), 6.68−6.78 (m, 5H, ArH), 6.81 (d, 2H, J = 6.9
Hz, ArH), 6.85−6.93 (m, 5H, ArH), 7.02 (t, 1H, J = 7.2 Hz, ArH),
7.15−7.19 (m, 5H, ArH), 7.31−7.42 (m, 2H, ArH), 7.53 (t, 1H, J =
7.5 Hz, ArH), 7.67 (d, 1H, J = 8.4 Hz, ArH), 7.83 (d, 1H, J = 8.4 Hz,
ArH), 7.95−8.02 (m, 3H, ArH), 8.05 (d, 1H, J = 8.4 Hz, ArH), 8.18
(d, 1H, J = 8.4 Hz, ArH); 31P NMR (CDCl3, 121 MHz, 85% H3PO4) δ
−12.78; MS (ESI) m/z (%) 869.7 (100) [M+ + 1]; HRMS (MALDI)
calcd for C58H50N2O2PS+ (M+ + 1) requires 869.3357, found
requires 737.2382, found 737.2386. [α]20 = +49.4 (c 0.90, CHCl3).
D
Preparation of Palladium Complex A from Ligand L1 with
PdCl2(PhCN)2. Ligand L1 (41 mg, 0.05 mmol) and bis(benzonitrile)
palladium dichloride (19 mg, 0.05 mmol) were dissolved in
dichloromethane (1.0 mL) under an argon atmosphere, and the
reaction mixture was stirred for 1 h at room temperature. Degassed
hexane (5.0 mL) was then slowly added, which led to the precipitation
of the formed complex. The mother liquor was filtered off, and the
precipitate was washed with hexane (2 × 1.0 mL) to afford the (R)-
(+)-complex A as an orange powder (41 mg, 91% yield). The single
crystal for X-ray diffraction was obtained by recrystallization from
chloroform.
869.3325. [α]20 = +45.8 (c 0.40, CHCl3).
D
(4S,5S)-2-((R)-2′-(Bis(3,5-dimethoxyphenyl)phosphino)-1,1′-bi-
naphthyl-2-yl)-4,5-diphenyl-1-tosyl-4,5-dihydro-1H-imidazoline,
L6. Yield: 185 mg, 66% for two steps; pale yellow solid, mp 156−159
°C; IR (CH2Cl2) ν 3403, 3295, 3155, 2993, 2725, 1825, 1769, 1642,
1595, 1479, 1333, 1306, 1277, 1219, 1205, 1185, 1167, 1009, 958, 858
1
cm−1; H NMR (CDCl3, TMS, 300 MHz) δ 2.27 (s, 3H, CH3), 3.37
Pd(L1)Cl2. Yield: 41 mg, 91%; yellow powder, mp 310−312 °C; IR
(CH2Cl2) ν 3059, 2968, 2904, 2362, 1622, 1585, 1484, 1438, 1354,
1268, 1172, 1130, 1084, 999, 967, 866, 818, 757, 712, 699, 594, 573,
(s, 6H, OCH3), 3.49 (s, 6H, OCH3), 4.46 (d, 1H, J = 6.0 Hz, CH),
4.58 (d, 1H, J = 6.0 Hz, CH), 5.79 (d, 2H, J = 7.8 Hz, ArH), 6.00 (dd,
2H, J1 = 2.4 Hz, J2 = 8.4 Hz, ArH), 6.18−6.24 (m, 2H, ArH), 6.33 (dd,
2H, J1 = 2.4 Hz, J2 = 7.5 Hz, ArH), 6.62 (d, 1H, J = 8.1 Hz, ArH),
6.76−6.93 (m, 7H, ArH), 7.00 (t, 1H, J = 7.5 Hz, ArH), 7.14−7.20 (m,
5H, ArH), 7.30−7.37 (m, 2H, ArH), 7.51−7.60 (m, 2H, ArH), 7.82
(d, 1H, J = 8.7 Hz, ArH), 7.91 (d, 1H, J = 8.1 Hz, ArH), 7.97−8.08
(m, 3H, ArH), 8.16 (d, 1H, J = 8.1 Hz, ArH); 31P NMR (CDCl3, 121
MHz, 85% H3PO4) δ −8.80; MS (ESI) m/z (%) 934.0 (100) [M+ +
1]; HRMS (MALDI) calcd for C58H50N2O6PS+ (M+ + 1) requires
1
533, 490 cm−1; H NMR (CDCl3, TMS, 400 MHz) δ 2.46 (s, 3H,
CH3), 4.25 (d, 1H, J = 10.4 Hz, CH), 4.57 (d, 1H, J = 10.4 Hz, CH),
5.58 (d, 2H, J = 6.8 Hz, ArH), 6.11 (d, 1H, J = 8.4 Hz, ArH), 6.67−
6.74 (m, 3H, ArH), 6.86−6.92 (m, 3H, ArH), 7.10 (t, 1H, J = 7.6 Hz,
ArH), 7.15 (dd, 2H, J1 = 1.6 Hz, J2 = 7.6 Hz, ArH), 7.19−7.25 (m, 2H,
ArH), 7.27−7.36 (m, 6H, ArH), 7.38−7.50 (m, 7H, ArH), 7.60 (d,
1H, J = 8.4 Hz, ArH), 7.63−7.73 (m, 3H, ArH), 7.91 (d, 1H, J = 8.0
Hz, ArH), 8.11 (t, 2H, J = 9.6 Hz, ArH), 8.34 (dd, 2H, J1 = 8.4 Hz, J2 =
14.4 Hz, ArH); 31P NMR (CDCl3, 162 MHz, 85% H3PO4) δ 22.94;
MS (MALDI) m/z (%) 953.1 (98.10) [M+ + 1]; HRMS (MALDI)
calcd for C54H41N2O2PSCl102Pd+ (M+ + 1) requires 949.1379, found
20
933.3131, found 933.3122. [α]D = +47.0 (c 0.20, CHCl3).
(4S,5S)-2-((R)-2′-(Bis(4-fluorophenyl)phosphino)-1,1′-binaphthyl-
2-yl)-4,5-diphenyl-1-tosyl-4,5-dihydro-1H-imidazoline, L7. Yield:
226 mg, 55% for two steps; pale yellow solid, mp 141−143 °C; IR
(CH2Cl2) ν 3060, 2926, 1640, 1587, 1493, 1454, 1371, 1341, 1306,
1266, 1227, 1161, 1088, 1058, 1016, 963, 816, 775, 739, 699, 668, 638,
949.1366. [α]20 = +402.7 (c 1.00, CHCl3).
D
General Procedure for the Reaction of 1,3-Diphenylpro-
penyl Acetate with Dimethyl Malonate in the Presence of
[Pd(η3-C3H5)Cl]2 and Chiral Imidazoline−Phosphine Ligand
L1. A solution of 1,3-diphenylpropenyl acetate (25 mg, 0.1 mmol),
enantiomerically pure ligand L1 (8.1 mg, 0.01 mmol, 10 mol %), and
allyl chloride palladium dimer [Pd(η3-C3H5)Cl]2 (1.8 mg, 0.005 mmol,
5 mol %) in solvent (0.5 mL) was stirred at room temperature for 30
min. To the solution were added dimethyl malonate (35 μL, 0.3 mmol,
3 equiv) and bis(trimethylsilyl)acetamide (73 μL, 0.3 mmol, 3 equiv),
and the reaction was monitored by TLC plates until 1,3-
diphenylpropenyl acetate was consumed completely. The reaction
1
611 cm−1; H NMR (CDCl3, TMS, 400 MHz) δ 2.28 (s, 3H, CH3),
4.45 (d, 1H, J = 6.4 Hz, CH), 4.54 (d, 1H, J = 6.4 Hz, CH), 5.84 (d,
2H, J = 7.2 Hz, ArH), 6.61 (d, 1H, J = 7.2 Hz, ArH), 6.67−6.73 (m,
4H, ArH), 6.77−6.94 (m, 9H, ArH), 7.00−7.08 (m, 3H, ArH), 7.18−
7.22 (m, 5H, ArH), 7.34−7.38 (m, 2H, ArH), 7.43 (dd, 1H, J1 = 2.4
Hz, J2 = 8.4 Hz, ArH), 7.55−7.60 (m, 1H, ArH), 7.79 (d, 1H, J = 8.4
Hz, ArH), 7.93 (d, 1H, J = 8.4 Hz, ArH), 7.98−8.06 (m, 3H, ArH),
8.17 (d, 1H, J = 8.4 Hz, ArH); 31P NMR (CDCl3, 162 MHz, 85%
H3PO4) δ −16.76; 19F NMR (CDCl3, 376 MHz, CFCl3) δ −112.92,
6473
dx.doi.org/10.1021/om2008309 | Organometallics 2011, 30, 6466−6475

Organometallics
Article
was quenched by the addition of a saturated NH4Cl aqueous solution,
and the product was extracted with CH2Cl2 (3 × 4 mL). The
combined organic layers were dried over anhydrous Na2SO4, filtered,
and concentrated in vacuo to yield the crude product, which was
purified by flash chromatography on silica gel (eluent: PE/EtOAc =
20:1) to furnish dimethyl(1,3-diphenyl-2-propen-1-yl)malonate as a
colorless oil.
(E)-4-Fluoro-1,3-diphenyl-4,4-bis(phenylsulfonyl)but-1-ene (8).
The ee was determined by chiral HPLC (Daicel CHIRALPACK
AD-H, hexane/iPrOH = 80:20, 1.0 mL/min, 254 nm): tmajor = 27.1
min, tminor = 20.1 min. [α]20D = −6.6 (c 1.30, CHCl3) {ref 7f [α]20
=
D
1
+13.8; c 1.54, CHCl3; 96% ee}. Colorless solid, mp 126−128 °C; H
NMR(CDCl3, TMS, 300 MHz) δ 4.66 (dd, 1H, J1 = 7.2 Hz, J2 = 11.1
Hz, CH), 6.43 (d, 1H, J = 12.0 Hz, CH), 7.01 (dd, 1H, J1 = 7.2 Hz,
J2 = 12.0 Hz, CH), 7.06−7.12 (m, 3H, ArH), 7.17−7.28 (m, 7H,
ArH), 7.36−7.50 (m, 7H, ArH), 7.56−7.66 (m, 1H, ArH), 7.78−7.95
(m, 2H, ArH); 13C NMR (CDCl3, TMS, 75 MHz) δ 29.7, 122.8,
122.9, 126.8, 128.0, 128.1, 128.4, 128.5, 128.6, 129.0, 130.4, 130.5,
130.9, 131.0, 134.4, 134.8, 135.3, 136.0, 136.7, 136.9; 19F NMR
(CDCl3, 212 MHz, CFCl3) δ −129.2.
(E)-Dimethyl 2-(1,3-diphenylallyl)malonate (7aa). The ee was
determined by chiral HPLC (Daicel CHIRALPACK AD-H, hexane/
iPrOH = 90:10, 0.7 mL/min, 254 nm): tminor = 25.8 min, tmajor = 18.5
min. [α]20D = +14.0 (c 1.00, CHCl3) {ref 12 [α]20D = +19.2; c = 1.30,
1
CHCl3; 95% ee}. H NMR (CDCl3, TMS, 400 MHz) δ 3.51 (s, 3H,
CH3), 3.70 (s, 3H, CH3), 3.95 (d, 1H, J = 10.8 Hz, CH), 4.27 (dd, 1H,
J1 = 8.8 Hz, J2 = 10.8 Hz, CH), 6.33 (dd, 1H, J1 = 8.8 Hz, J2 = 15.6 Hz,
=CH), 6.48 (d, 1H, J = 15.6 Hz, CH), 7.17−7.25 (m, 3H, ArH),
7.26−7.34 (m, 7H, ArH).
(E)-Diethyl 2-(1,3-diphenylallyl)malonate (7ab). The ee was
determined by chiral HPLC (Daicel CHIRALPACK IA-H, hexane/
iPrOH = 90:10, 0.5 mL/min, 254 nm): tminor = 20.4 min, tmajor = 16.1
min. [α]20D = +17.2 (c 1.40, CHCl3) {ref 13 [α]25D = −17.2; c = 1.02,
CHCl3; 97% ee}. 1H NMR (CDCl3, TMS, 300 MHz) δ 1.06 (t, 3H, J
= 7.2 Hz, CH3), 1.20 (t, 3H, J = 7.2 Hz, CH3), 3.85 (d, 1H, J = 11.1
Hz, CH), 4.13−4.25 (m, 5H, CH2, CH), 6.28 (dd, 1H, J1 = 8.1 Hz, J2
=15.6 Hz, CH), 6.39 (d, 1H, J = 15.6 Hz, CH), 7.15−7.19 (m,
5H, ArH), 7.37−7.46 (m, 5H, ArH).
ASSOCIATED CONTENT
* Supporting Information
■
S
Spectroscopic charts and chiral HPLC traces of the products
shown in Tables 1−4, X-ray crystal data of palladium complex
A as well as detailed descriptions of experimental procedures.
This material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: Mshi@mail.sioc.ac.cn. Fax: 86-21-64166128.
■
(E)-Dimethyl(1,3-bis(4-methylphenyl)-2-propen-1-yl)malonate
(7ba). The ee was determined by chiral HPLC (Daicel CHIR-
ALPACK AD-H, hexane/iPrOH = 94:6, 0.5 mL/min, 254 nm): tminor
ACKNOWLEDGMENTS
= 50.0 min, tmajor= 34.5 min. [α]20 = +13.0 (c 1.50, CHCl3) {ref 14
■
D
1
[α]20 = −13.4; c = 1.0, CHCl3; 80% ee}. H NMR (CDCl3, TMS,
We thank the Shanghai Municipal Committee of Science and
Technology (08dj1400100-2), National Basic Research Pro-
gram of China (973)-2010CB833302, and the National Natural
Science Foundation of China for financial support (21072206,
20472096, 20902019, 20872162, 20672127, 20821002,
20732008, and 20702059), and we also thank Mr. Jie Sun for
X-ray diffraction.
D
300 MHz) δ 2.30 (s, 6H, CH3), 3.52 (s, 3H, CH3), 3.68 (s, 3H, CH3),
3.92 (d, 1H, J = 10.8 Hz, CH), 4.21 (dd, 1H, J1 = 8.7 Hz, J2 = 10.8 Hz,
CH), 6.25 (dd, 1H, J1 = 8.7 Hz, J2 = 15.9 Hz, CH), 6.43 (d, 1H, J =
15.9 Hz, CH), 7.05−7.13 (m, 4H, ArH), 7.16−7.25 (m, 4H, ArH).
(E)-Dimethyl(1,3-bis(4-chlorophenyl)-2-propen-1-yl)malonate
(7ca). The ee was determined by chiral HPLC (Daicel CHIR-
ALPACK AD-H, hexane/iPrOH = 85:15, 0.8 mL/min, 254 nm): tminor
= 36.5 min, tmajor = 23.4 min. [α]20 = +1.4 (c 1.65, CHCl3) {ref 14
D
[α]20D = −3.1; c = 1.0, CHCl3; 97% ee}. 1H NMR (CDCl3, TMS, 300
MHz) δ 3.55 (s, 3H, CH3), 3.70 (s, 3H, CH3), 3.90 (d, 1H, J = 10.8
Hz, CH), 4.24 (dd, 1H, J1 = 8.4 Hz, J2 = 10.8 Hz, CH), 6.26 (dd, 1H,
J1 = 8.4 Hz, J2 = 15.9 Hz, CH), 6.41 (d, 1H, J = 15.9 Hz, CH),
7.21−7.32 (m, 8H, ArH).
REFERENCES
■
(1) (a) Miyashita, A.; Yasuda, H.; Takaya, K.; Toriumi, T.; Ito, T.;
Noyori, R. J. Am. Chem. Soc. 1980, 102, 7932−7934. (b) Noyori, R.;
Takaya, H. Acc. Chem. Res. 1990, 23, 345−350. (c) Noyori, R.; Suga,
S.; Kawai, K.; Okada, S.; Kitamura, M. Pure Appl. Chem. 1988, 60,
1597−1606. (d) Noyori, R. Chem. Soc. Rev. 1989, 18, 187−208.
(2) (a) Uozumi, Y.; Hayashi, T. J. Am. Chem. Soc. 1991, 113, 9887−
9888. (b) Uozumi, Y.; Tanahashi, A.; Lee, S.-Y.; Hayashi, T. J. Org.
Chem. 1993, 58, 1945−1948. (c) Uozumi, Y.; Kitayama, K.; Hayashi,
T.; Yanagi, K.; Fukuyo, E. Bull. Chem. Soc. Jpn. 1995, 68, 713−722.
(3) (a) MOP (X = OMe) was developed by Hayashi and co-
(E)-Dimethyl(1,3-bis(4-bromophenyl)-2-propen-1-yl)malonate
(7da). The ee was determined by chiral HPLC (Daicel CHIR-
ALPACK IA-H, hexane/iPrOH = 90:10, 0.7 mL/min, 254 nm): tminor
= 28.1 min, tmajor = 18.2 min. [α]20 = −1.1 (c = 0.4, CHCl3) {ref 14
D
1
[α]20 = +3.0; c 1.0, CHCl3; 97% ee}. H NMR (CDCl3, TMS, 300
D
MHz) δ 3.55 (s, 3H, CH3), 3.70 (s, 3H, CH3), 3.89 (d, 1H, J = 10.8
Hz, CH), 4.22 (dd, 1H, J1 = 8.1 Hz, J2 = 10.8 Hz, CH), 6.27 (dd, 1H,
J1 = 8.1 Hz, J2 = 15.9 Hz, CH), 6.39 (d, 1H, J = 15.9 Hz, CH),
7.15−7.18 (m, 4H, ArH), 7.38−7.47 (m, 4H, ArH).
workers; see ref 2. (b) MAP (X = NMe2): Vyskoci
̌ ̌
l, S.; Smrcina, M.;
Hanus, V.; Polasek, M.; Kocovsky, P. J. Org. Chem. 1998, 63, 7738−
̌
́
7748. Ding, K.-L.; Wang, Y.; Yun, H.; Liu, J.; Wu, Y.; Terada, M.;
Okubo, Y.; Mikami, K. Chem.Eur. J. 1999, 5, 1734−1737. (c)
BINAPS (X = SMe): Kang, J.; Yu, S.-H.; Kim, J. I.; Cho, H. G. Bull.
Korean Chem. Soc. 1995, 16, 439−443. Gladiali, S.; Medici, S.; Pirri, G.;
Pulacchini, S.; Fabbri, D. Can. J. Chem. 2001, 79, 670−678. (d)
Ligand LB in which X = AsPh2: Cho, S. Y.; Shibasaki, M. Tetrahedron
Lett. 1998, 13, 1773−1776. Ligand LB in which X = P(O)Ph2:
(e) Gladiali, S.; Pulacchini, S.; Fabbri, D.; Manassero, M.; Sansoni, M.
Tetrahedron: Asymmetry 1998, 9, 391−395. Ligand LB in which X =
P(S)Ph2: (f) Faller, J. W.; Wilt, J. C.; Parr, J. Org. Lett. 2004, 6, 1301−
1304. TolBINAP: (g) Gladiali, S.; Dore, A.; Fabbri, D.; Medici, S.;
Pirri, G.; Pulacchini, S. Eur. J. Org. Chem. 2000, 16, 2861−2865.
(4) Yan, Y.-J.; Zhang, X. -M. J. Am. Chem. Soc. 2006, 128, 7198−
7202.
General Procedure for the Reaction of 1,3-Diphenylpro-
penyl Acetate with 1-Fluorobis(phenylsulfonyl)methane in
the Presence of [Pd(η3-C3H5)Cl]2 and Chiral Imidazoline−
Phosphine Ligand L7. A solution of 1,3-diphenylpropenyl acetate
(25 mg, 0.1 mmol), enantiomerically pure ligand L7 (8.5 mg, 0.01
mmol, 10 mol %), and allyl chloride palladium dimer [Pd(η3-
C3H5)Cl]2 (1.8 mg, 0.005 mmol, 5 mol %) in solvent (0.5 mL) was
stirred at room temperature for 5 min. To the solution were added 1-
fluorobis(phenylsulfonyl)methane (35 mg, 0.11 mmol) and Cs2CO3
(36 mg, 0.11 mmol). The resulting solution was stirred at room
temperature for 12 h, when 1,3-diphenylpropenyl acetate was
completely consumed, as indicated by TLC analysis. The reaction
mixture was poured into saturated NH4Cl, and it was extracted with
CH2Cl2. The organic phase was dried over anhydrous sodium sulfate.
After evaporation of the solvent under reduced pressure, the product
was purified by silica gel column chromatography to give 8 as a
colorless solid.
(5) (a) Sakai, N.; Mano, S.; Nozaki, K.; Takaya, H. J. Am. Chem. Soc.
1993, 115, 7033−7034. (b) Nozaki, K.; Sakai, N.; Nanno, T.;
Higashijima, T.; Mano, S.; Horiuchi, T.; Takaya, H. J. Am. Chem. Soc.
1997, 119, 4413−4423. (c) Horiuchi, T.; Takaya, H. J. Org. Chem.
6474
dx.doi.org/10.1021/om2008309 | Organometallics 2011, 30, 6466−6475

Organometallics
Article
1997, 62, 4285−4292. (d) Nozaki, K.; Kawashima, Y.; Hiyama, T.;
Matsubara, T. J. Am. Chem. Soc. 2001, 23, 534−544. (e) Solinas, M.;
Marchetti, M. J. Mol. Catal. A: Chem. 2005, 226, 141−147. (f) Nozaki,
K.; Hiyama, T. Adv. Synth. Catal. 2001, 343, 61−63. (g) Horiuchi, T.;
Takaya, H. Organometallics 1997, 16, 2981−2986. (h) Nozaki, K.; Li,
W.-G.; Takaya, H. Tetrahedron Lett. 1997, 38, 4611−4614. (i) Nozaki,
K.; Li, W.-G.; Miura, T.; Kumobayashi, H. J. Org. Chem. 1996, 61,
7658−7659. (j) Nanno, T.; Sakai, N.; Nozaki, K.; Takaya, H.
Tetrahedron: Asymmetry 1995, 6, 2583−2591.
90°, γ = 90°, V = 5758.8(8) Å3; space group: P2(1)2(1)2(1); Z = 4;
Dcalc = 1.555 g/cm3; F000 = 2720; final R indices [I > 2σ(I)] R1 =
0.0281, wR2 = 0.653.
(6) (a) Deng, H.-P.; Wei, Y.; Shi, M. Adv. Synth. Catal. 2009, 351,
2897−2902. (b) Ogasawara, M.; Yoshida, K.; Kamei, H.; Kato, K.;
Uozumi, Y.; Hayashi, T. Tetrahedron: Asymmetry 1998, 9, 1779−1787.
(c) Hatano, M.; Yamanaka, M.; Mikami, K. Eur. J. Org. Chem. 2003,
2552−2555. (d) Uozumi, Y.; Suzuki, N.; Ogiwara, A.; Hayashi, T.
Tetrahedron 1994, 50, 4293−4302. (e) Zhao, Q.-Y.; Yuan, Z.-L.; Shi,
M. Tetrahedron: Asymmetry 2010, 21, 943−951. (f) Imai, Y.; Zhang,
W.-B.; Kida, T.; Nakatsuji, Y.; Ikeda, I. Tetrahedron Lett. 1998, 39,
4343−4346. (g) Selvakumar, K.; Valentini, M.; Pregosin, P. S.;
Albinati, A. Organometallics 1999, 18, 1207−1215. (h) Zhao, Q.-Y.;
Shi, M. Tetrahedron 2011, 67, 3724−3732.
(7) For recent reviews, see: (a) Trost, B. M.; Van Vranken, D. L.
Chem. Rev. 1996, 96, 395−422. (b) Pfaltz, A.; Lautens, M. In
Comprehensive Asymmetric Catalysis; Jacobsen, E. N.; Pfaltz, A.;
Yamamoto, H., Eds.; Springer-Verlag: Berlin, 1999; Vol. 2, Chapter
24. (c) Helmchen, G.; Pfaltz, A. Acc. Chem. Res. 2000, 33, 336−345.
(d) Trost, B. M.; Crawley, M. L. Chem. Rev. 2003, 103, 2921−2944.
(e) Lu, Z.; Ma, S.-M. Angew. Chem., Int. Ed. 2008, 47, 258−297.
(f) Fukuzumi, T.; Shibata, N.; Sugiura, M.; Yasui, H.; Nakamura, S.;
Toru, T. Angew. Chem., Int. Ed. 2006, 45, 4973−4977. (g) Liu, W.-B.;
Zheng, S.-C.; He, H.; Zhao, X.-M.; Dai, L.-X.; You, S.-L. Chem.
Commun. 2009, 6604−6606.
(8) (a) Ghosh, A. K.; Mathivanan, P.; Cappiello, J. Tetrahedron:
Asymmetry 1998, 9, 1−45. (b) Gomez, M.; Muller, G.; Rocamora, M.
́
Coord. Chem. Rev. 1999, 193−195, 769. (c) McManus, H. A.; Guiry, P.
J. Chem. Rev. 2004, 104, 4151−4202. (d) Zhou, J.; Tang, Y. Chem. Soc.
Rev. 2005, 34, 664−676. (e) Desimoni, G.; Faita, G.; JΦrgensen, K. A.
Chem. Rev. 2006, 106, 3561−3651.
(9) Liu, H.; Du, D.-M. Adv. Synth. Catal. 2009, 351, 489−519.
(10) For selected examples, see: (a) Busacca, C. A.; Grossbach, D.;
So, R. C.; O'Brien, E. M.; Spinelli, E. M. Org. Lett. 2003, 5, 595−598.
́
(b) Bastero, A.; Ruiz, A.; Claver, C.; Castillon, S. Eur. J. Inorg. Chem.
2001, 3009−3011. (c) Bastero, A.; Ruiz, A.; Claver, C.; Milani, B.;
Zangrando, E. Organometallics 2002, 21, 5820−5829. (d) Bastero, A.;
Claver, C.; Ruiz, A.; Castillón, S.; Daura, E.; Bo, C.; Zangrando, E.
Chem.Eur. J. 2004, 10, 3747−3760. (e) Casey, M.; Smyth, M. P.
Synlett 2003, 102−106. (f) Du, X.; Liu, H.; Du, D.-M. Eur. J. Org.
Chem. 2011, 786−793.
(11) (a) You, S.-L.; Kelly, J. W. Org. Lett. 2004, 6, 1681−1683.
(b) Liu, H.; Du, D.-M. Adv. Synth. Catal. 2010, 353, 1113−1118.
(c) Wang, X.-Q.; Xia, J.-B.; Dai, X.-Y.; You, S.-L. Sci. China, Ser. B:
Chem. 2009, 52, 1331−1336.
(12) Leutenegger, U.; Umbricht, G.; Fahrni, C.; Matt, P. V.; Pfaltz, A.
Tetrahedron 1992, 48, 2143−2156.
(13) Tanaka, Y.; Mino, T.; Akita, K.; Sakamoto, M.; Fujita, T. J. Org.
Chem. 2004, 69, 6679−6687.
(14) Kinoshita, N.; Kawabata, T.; Tsubaki, K.; Bando, M.; Fuji, K.
Tetrahedron 2006, 62, 1756−1763.
(15) For selected examples, see: (a) Sun, Y.-W.; Jiang, J.-J.; Zhao,
M.-X.; Wang, F.-J.; Shi, M. J. Organomet. Chem. 2011, 696, 2850−
2856. (b) Chiang, W.-Y.; Hong, F.-E. J. Organomet. Chem. 2009, 694,
1473−1481. (c) Thiesen, K. E.; Maitra, K.; Olmstead, M. M.; Attar, S.
Organometallics 2010, 29, 6334−6342. (d) Dyer, P. W.; Fawcett, J.;
Hanton, M. J. J. Organomet. Chem. 2005, 690, 5264−5281.
(16) The crystal data of Pd(L1)Cl2 have been deposited in the
CCDC with number 826453. Empirical formula:
C57H44Cl11N2O2PPdS; formula weight: 1348.32; crystal color, habit:
colorless; crystal dimensions: 0.22 × 0.15 × 0.12 mm; crystal system:
orthorhombic; lattice type: primitive; lattice parameters: a =
10.6194(9) Å, b = 19.4491(16) Å, c = 27.882(2) Å, α = 90°, β =
6475
dx.doi.org/10.1021/om2008309 | Organometallics 2011, 30, 6466−6475