Enhanced catalytic activity in asymmetric hydrosilylation of 1,3-dienes with a soluble palladium catalyst

Article abstract of DOI:10.1016/S0957-4166(02)00094-0

A new MOP ligand 8 containing two n-octyl groups at the 6 and 6′ positions of the (R)-2-(diphenylphosphino)-2′-aryl-1,1′-binaphthyl skeleton was prepared and used for the palladium-catalyzed asymmetric hydrosilylation of 1,3-dienes with trichlorosilane. T

Full text of DOI:10.1016/S0957-4166(02)00094-0

TETRAHEDRON:
ASYMMETRY
Pergamon
Tetrahedron: Asymmetry 13 (2002) 325–331
Enhanced catalytic activity in asymmetric hydrosilylation of
1,3-dienes with a soluble palladium catalyst
Jin Wook Han and Tamio Hayashi*
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan
Received 19 February 2002; accepted 21 February 2002
Abstract—A new MOP ligand 8 containing two n-octyl groups at the 6 and 6% positions of the (R)-2-(diphenylphosphino)-2%-aryl-
1,1%-binaphthyl skeleton was prepared and used for the palladium-catalyzed asymmetric hydrosilylation of 1,3-dienes with
trichlorosilane. The introduction of the n-octyl groups made the palladium–phosphine catalyst soluble in the reaction system,
realizing high catalytic activity at a low reaction temperature. As a result, ligand 8 showed highest enantioselectivity for both
cyclic and linear 1,3-dienes. © 2002 Elsevier Science Ltd. All rights reserved.
palladium complex coordinated with the Ar-MOP lig-
and is not high enough due mainly to the low solubility
of its palladium complex in the reaction media consist-
ing of a diene and trichlorosilane. Although the concept
of introducing a long-chain alkyl group to increase
solubility has often appeared in polymer chemistry,10,11
there have been few reports in the field of homogeneous
asymmetric catalysis.12 Here we wish to report that
appropriate modification of the Ar-MOP ligand by
introducing a long-chain alkyl group at the 6 and 6%
positions of binaphthyl leads to the higher catalytic
activity and enantioselectivity for 1,3-dienes.13
1. Introduction
Enantiomerically enriched allylsilanes are useful chiral
reagents for organic synthesis and their preparation by
asymmetric catalysis attracts increasing attention.1
They have been prepared by one of the four types of
palladium-catalyzed asymmetric reactions, i.e. (1) asym-
metric cross-coupling of 1-silylalkyl Grignard reagents
with alkenyl bromides,2 (2) asymmetric reduction of
silyl-substituted allylic carbonates with formic acid,3 (3)
asymmetric silylation of allylic chlorides with a disi-
lane,4 and (4) asymmetric hydrosilylation of 1,3-
dienes.5–8 Of these catalytic methods, asymmetric
hydrosilylation has advantages over the others in that
(a) the starting materials, hydrosilane and 1,3-dienes,
are readily accessible, (b) the hydrosilylation does not
require any solvents, (c) it proceeds with a low catalyst
loading, and (d) silafunctional allylsilanes can be
obtained. The development of palladium-catalyzed
asymmetric hydrosilylation has been dependent upon
the development of chiral monophosphine ligands with
higher enantioselectivity. No chelating bisphosphine–
palladium complexes can be used because of their low
catalytic activity. The most enantioselective ligand so
far reported for the palladium-catalyzed hydrosilylation
of 1,3-dienes is (R)-2-(diphenylphosphino)-2%-(3,5-
dimethyl-4-methoxyphenyl)-1,1%-binaphthyl (Ar-MOP,
1),7c,9 which gave the corresponding allylsilane of 90%
ee in the hydrosilylation of cyclopentadiene with
trichlorosilane.7c However, the catalytic activity of the
2. Results and discussion
A synthetic route to the Ar-MOP ligand which contains
n-octyl groups at the 6 and 6% positions of 1,1%-binaph-
thyl is outlined in Scheme 1. The n-octyl group was
introduced by the palladium-catalyzed Grignard cross-
coupling
of
(R)-6,6%-dibromo-2,2%-diethoxy-1,1%-
binaphthyl14 2. Thus, the reaction of 2 with an excess of
n-octylmagnesium bromide in the presence of
PdCl2(dppf)15 as a catalyst in ether gave 91% yield of
(R)-2,2%-diethoxy-6,6%-dioctyl-1,1%-binaphthyl 3, which
* Corresponding author.
0957-4166/02/$ - see front matter © 2002 Elsevier Science Ltd. All rights reserved.
PII: S0957-4166(02)00094-0

326
J. W. Han, T. Hayashi / Tetrahedron: Asymmetry 13 (2002) 325–331
media than with Ar-MOP ligand 1, was examined for
its catalytic activity and enantioselectivity in the asym-
metric hydrosilylation of cyclic 1,3-dienes 9a and 9b
with trichlorosilane (Scheme 2). The reaction was car-
ried out without solvent in the presence of 0.25 mol%
of the palladium catalyst generated in situ by mixing
[PdCl(p-C3H5)]2 with 2 equiv. (to palladium) of chiral
ligand 8. The hydrosilylation products, allyl-
(trichloro)silanes 10a and 10b, were allowed to react
with benzaldehyde in DMF according to Kobayashi’s
procedure17 to give the corresponding homoallylic alco-
hols 11, which were subjected to the HPLC analysis
with a chiral stationary phase column for determination
of the enantioselectivity. The results are summarized in
Table 1, which also contains the data obtained7c with
(R)-Ar-MOP 1 for comparison. In the reaction of
1,3-cyclohexadiene 9a, the highest enantioselectivity so
far recorded was 79% ee, which was observed with
Ar-MOP ligand 1 at 0°C (entry 1 in Table 1). At a
lower temperature, the hydrosilylation of 9a did not
proceed at all even if the reaction time was prolonged,
due to the insolubility of the palladium catalyst coordi-
nated with ligand 1 in the reaction media consisting of
1,3-cyclohexadiene 9a and trichlorosilane (entry 3 in
Table 1). As shown in Fig. 1, considerable amounts of
off-white precipitates were observed in the reaction
flask containing the palladium catalyst coordinated
with the Ar-MOP ligand 1. On the other hand, the
palladium catalyst of the new ligand 8 was soluble in
the reaction media, forming a clear solution even at
–10°C. As a result, the hydrosilylation of 9a was cata-
lyzed by the palladium/8 at −10°C to give (S)-3-
trichlorosilylcyclohexene 10a with 83% ee, which is the
highest value for the reaction of 9a (entry 4 in Table 1).
The enantioselectivity of the Ar-MOP ligands was not
influenced greatly by introduction of the n-octyl group,
which is shown by essentially the same stereochemical
outcome obtained in the hydrosilylation at 0°C (entries
1 and 2 in Table 1). The highest enantioselectivity was
Scheme 1. Preparation of ligand 8 containing n-octyl groups
at the 6 and 6% positions of binaphthyl. (a) n-C8H17MgBr,
PdCl2(dpp), ether, 50°C, 20 h, 91%; (b) BBr3, CH2Cl2, 12 h,
95%; (c) Tf2O, py, CH2Cl2, 2 h, 95%; (d) Ph2POH, Pd(OAc)2,
dppb, i-Pr2NEt, DMSO, 130°C, 18 h, 78%; (e) HSiCl3, Et3N,
xylene, 100°C, 12 h, 93%; (f) 3,5-Me2-4-MeOC6H2MgBr,
NiCl2(PPh3)2, THF, 80°C, 24 h, 80%.
was treated with BBr3 for the deprotection of ethyl
ether to give (R)-6,6%-dioctyl-2,2%-dihydroxy-1,1%-
naphthyl11 4 in 95% yield. Friedel–Crafts acylation
followed by reduction of carbonyl is also a useful
method for this transformation.11 The conversion of 4
into (R)-2-diphenylphosphino-2%-(3,5-dimethyl-4-meth-
oxyphenyl)-6,6%-dioctyl-1,1%-binaphthyl 8 was achieved
in a high yield by the four-step reactions according
to the procedures reported for Ar-MOP ligand 1.7c,16 In
the course of the transformations, the n-octyl group on
the binaphthyl skeleton did not interfere with the reac-
tions. Thus, the selective monophosphinylation of the
ditriflate 5, readily obtained by treatment of 4 with
Tf2O, with diphenylphosphine oxide in the presence of
a palladium catalyst at 130°C gave 78% yield of (R)-2-
diphenylphosphinyl-6,6%-dioctyl-2%-trifluoromethanesul-
fonyloxy-1,1%-binaphthyl 6. The reduction of phosphine
oxide in 6 with trichlorosilane followed by substitution
of the remaining triflate of 7 with 3,5-dimethyl-4-
methoxyphenyl group by the nickel-catalyzed Grignard
cross-coupling gave the n-octylated Ar-MOP ligand 8.
As expected, the introduction of two n-octyl groups
made ligand 8 much more soluble in non-polar solvents
such as hexane and diethyl ether than the original
Ar-MOP ligand 1.7c
A palladium catalyst coordinated with the n-octylated
Ar-MOP ligand 8, which is more soluble in the reaction
Scheme 2. Pd-catalyzed asymmetric hydrosilylation of cyclic
1,3-dienes.

J. W. Han, T. Hayashi / Tetrahedron: Asymmetry 13 (2002) 325–331
327
a
Table 1. Pd-catalyzed asymmetric hydrosilylation of cyclic 1,3-dienes with HSiCl3
Entry
Diene
Ligand (L*)
Temp. (°C)
Time (h)
Yieldb (%)
Eec (%)
Config.d
1
2
3
4
5
6
7
8
9a
9a
9a
9a
9b
9b
9b
9b
1
8
1
8
1
8
1
8
0
0
72
72
168
168
72
72
168
168
75
80
0
70
89
86
0
79
80
–
83
90
90
–
S
S
–
S
S
S
–
−10
−10
−20
−20
−30
−30
75
91
S
a The hydrosilylation was carried out without solvent. The catalyst was generated in situ by mixing [PdCl(p-C3H5)]2 and a chiral ligand 1 or 8.
The initial ratio of diene/HSiCl3/Pd/L* was 1.0/1.2/0.0025/0.0050.
b Isolated yield by bulb-to-bulb distillation.
c Determined by HPLC analysis of alcohol 11 with a chiral stationary column (Daicel Chiralpak OB-H) for 10.
d Determined by optical rotation of alcohols 11. For entry 2 (11a), [h]D20 +11.1 (c 0.82, benzene). For entry 6 (11b), [h]2D0 +27.2 (c 1.86, chloroform).
with KMnO4 and NaIO4 followed by esterification with
diazomethane gave 48% yield of (−)-methyl (2S,3S)-3-
hydroxy-2-methyl-3-phenylpropanoate 12 {[h]2D0 –16.4
(c 1.0, CHCl3)}, indicating that 11c has (1S,2R)
configuration. The R configuration of allylsilane 10c
was deduced from the assumption that the reaction of
allyl(trichloro)silane with aldehyde proceeds via a cyclic
transition state.17 At –10°C, the hydrosilylation of 9c by
palladium/1 was very slow, giving only 9% yield of the
product with 77% ee, which is also due to the insolubil-
ity of the palladium catalyst coordinated with ligand 1
in the reaction media (entry 3 in Table 2). The higher
Figure 1. The solubility of palladium catalysts coordinated
with ligand 1 (a) and ligand 8 (b).
catalytic activity of the palladium catalyst of the n-
octylated Ar-MOP ligand 8 is clearly demonstrated by
monitoring the reaction progress in the reaction of
1,3-decadiene with the palladium catalysts of ligand 1
and 8 (Fig. 2). With all other variables being constant,
hydrosilylation with ligand 8 was completed within 4 h,
while it took longer than 24 h with ligand 1. This
dramatic enhancement of catalytic reactivity with lig-
and 8 is attributed to the increased solubility of the
complex in the reaction media. Enantioselectivities for
linear 1,3-dienes appeared to show the same trend as
for cyclic dienes. That is, n-octyl group on the ligand
did not influence the stereochemical outcome in the
hydrosilylation of linear 1,3-dienes (entries 1 and 2,
entries 5 and 6 in Table 2). At a lower temperature,
higher enantioselectivities were observed with ligand 8
(entries 4 and 8 in Table 2). Notably, use of hexane as
solvent gave better results than without solvent in the
hydrosilylation6b of 1-phenyl-1,3-butadiene (9d) with
ligand 8 (entry 9 in Table 2).
also observed in the hydrosilylation of cyclopentadiene
9b by use of the n-octylated MOP ligand 8. Thus, the
reaction of 9b proceeded at –30°C in the presence of the
palladium/8 as a catalyst, to give (S)-3-trichlorosilylcy-
clopentene 10b of 91% ee (entry 8 in Table 1). Here
again, the reaction with ligand 1 did not take place at
the same temperature (entry 7 in Table 1).
The palladium catalysts coordinated with ligand 1 and
8 were also effective for the asymmetric hydrosilylation
of linear 1,3-dienes, (E)-1,3-decadiene 9c and (E)-1-
phenyl-1,3-butadiene 9d, with trichlorosilane (Scheme
3). The hydrosilylation took place in an exclusive 1,4-
fashion where the hydrogen and the silyl group are
attached to the 1 and 4 positions of diene, respectively,
to give (Z)-allyl(trichloro)silanes 10c and 10d with per-
fect regioselectivity. The results are summarized in
Table 2. The reaction of (E)-1,3-decadiene 9c with
trichlorosilane in the presence of palladium/1 catalyst at
20°C gave (R)-(Z)-4-(trichlorosilyl)-2-decene 10c in
81% isolated yield as a single regioisomer (entry 1 in
Table 2). The allylsilane, (R)-(Z)-10c, was allowed to
react with benzaldehyde in DMF to give (1S,2R)-(E)-2-
methyl-1-phenyl-3-decen-1-ol 11c {[h]2D0 −12.6 (c 1.1,
CHCl3), 69% ee}, of which enantiomeric purity was
determined by HPLC analysis with a chiral stationary
phase column. The relative and absolute stereochem-
istry of the homoallylic alcohol 11c was correlated with
that of known methyl 3-hydroxy-2-methyl-3-
phenylpropanoate18 12. Thus, oxidative cleavage of 11c
Scheme 3. Pd-catalyzed asymmetric hydrosilylation of linear
1,3-dienes.

328
J. W. Han, T. Hayashi / Tetrahedron: Asymmetry 13 (2002) 325–331
a
Table 2. Pd-catalyzed asymmetric hydrosilylation of linear 1,3-dienes with HSiCl3
Entry
Diene
Ligand (L*)
Temp. (°C)
Time (h)
Yieldb (%)
Eec (%)
Config.d
1
2
3
4
5
6
7
8
9e
9c
9c
9c
9c
9d
9d
9d
9d
9d
1
8
1
8
1
8
1
8
8
20
20
−10
−10
20
20
0
0
0
24
4
168
168
22
81
91
9
76
85
95
14
52
53
69
68
77
77
62
63
71
72
79
R
R
R
R
S
S
S
S
S
22
168
168
168
a The hydrosilylation was carried out without solvent. The catalyst was generated in situ by mixing [PdCl(p-C3H5)]2 and a chiral ligand 1 or 8.
The initial ratio of diene/HSiCl3/Pd/L* was 1.0/1.2/0.0025/0.0050.
b Isolated yield by bulb-to-bulb distillation.
c Determined by HPLC analysis of alcohol 11c and 11d with a chiral stationary column (Daicel Chiralpak AD and Daicel Chiralcel OD-H) for
10c and 10d, respectively.
d Determined by optical rotation of alcohols 11. For entry 1 (11c), [h]D20 −12.6 (c 1.1, chloroform). For entry 8 (11d), [h]2D0 +15.0 (c 1.1,
chloroform).14
e In hexane solvent.
by passage through P2O5. Optical rotations were mea-
sured with a Jasco DIP-370 polarimeter. NMR spectra
were recorded on a JEOL JNM LA-500 spectrometer
1
(500 MHz for H, 125 MHz for 13C, and 202 MHz for
31P). Chemical shifts are reported in l ppm referenced
1
to an internal tetramethylsilane standard for H NMR,
residual chloroform (l 77.00) for 13C, and external 85%
H3PO4 standard for 31P NMR. HPLC analysis was
performed on a Jasco PU-980 liquid chromatograph
system with a chiral stationary phase column, Daicel
Chiralpak OB-H, Chiralpak AD, or Chiralcel OD-H.
(R)-2-(Diphenylphosphino)-2%-(3,5-dimethyl-4-meth-
oxyphenyl)-1,1%-binaphthyl7c 1 and (R)-6,6%-dibromo-
Figure 2. Reaction profile in the hydrosilylation of 9c with
2,2%-diethoxy-1,1%-binaphthyl14 2 was prepared accord-
ligand 1 (a) and ligand 8 (b).
ing to the reported procedure.
4.1. (R)-2,2%-Diethoxy-6,6%-dioctyl-1,1%-binaphthyl 3
A
mixture of (R)-2,2%-dibromo-6,6%-diethoxy-1,1%-
3. Conclusion
binaphthyl 2 (1.1 g, 2.1 mmol), PdCl2(dppf) (0.032 g,
0.04 mmol), and n-octylmagnesium bromide (1.0 M, 7
mL, in diethyl ether) in 5 mL of diethyl ether was
refluxed for 20 h. After cooling to room temperature,
the reaction mixture was quenched with saturated
ammonium chloride and extracted with ethyl acetate.
The extract was dried over anhydrous MgSO4 and the
solvent was evaporated. The residue was chro-
matographed on silica gel (hexane/ethyl acetate=30/1)
to give 1.1 g (91% yield) of the titled compound as
We have shown that the palladium-catalyzed Grignard
cross-coupling is a useful method for introducing an
alkyl group onto the binaphthyl skeleton. The Ar-MOP
ligand 8 which contains two n-octyl groups at the 6 and
6% positions of binaphthyl was prepared and used for
the palladium-catalyzed asymmetric hydrosilylation of
1,3-dienes. The introduction of two n-octyl groups
made the palladium catalyst soluble in the hydrosilyla-
tion media. The high solubility of the chiral palladium
catalyst realized the hydrosilylation at a lower reaction
temperature, resulting in the higher enantioselectivity in
the asymmetric hydrosilylation of 1,3-dienes with
trichlorosilane.
1
colorless oil. H NMR (CDCl3) l 0.87 (t, J=6.1 Hz,
6H), 1.04 (t, J=7.0 Hz, 6H), 1.20–1.43 (m, 20H),
1.62–1.68 (m, 4H), 2.69 (t, J=7.8 Hz, 4H), 3.98–4.03
(m, 4H), 7.04 (s, 4H), 7.37 (d, J=8.9 Hz, 2H), 7.60 (s,
2H), 7.84 (d, J=8.9 Hz, 2H). 13C NMR (CDCl3) l
14.04, 15.00, 22.61, 29.39, 29.46, 31.26, 31.84, 35.81,
65.31, 116.04, 120.90, 125.44, 126.03, 127.63, 128.34,
129.42, 132.59, 137.81, 153.71. Anal. calcd for
C40H54O2: C, 84.75; H, 9.60. Found: C, 84.56; H, 9.74.
[h]2D0 +0.4 (c 1.3, CHCl3).
4. Experimental
All moisture-sensitive manipulations were carried out
under a nitrogen atmosphere. Nitrogen gas was dried

J. W. Han, T. Hayashi / Tetrahedron: Asymmetry 13 (2002) 325–331
329
4.2. (R)-6,6%-Dioctyl-1,1%-bi-2-naphthol 4
was dried over anhydrous MgSO4 and the solvent was
evaporated. The residue was chromatographed on silica
gel (hexane/ethyl acetate=5/1) to give 1.5 g (78% yield)
of the titled compound as colorless oil. 1H NMR
(CDCl3) l 0.85–0.89 (m, 6H), 1.19–1.43 (m, 20H),
1.62–1.73 (m, 4H), 2.69 (t, J=8.0 Hz, 2H), 2.74 (t,
J=8.0 Hz, 2H), 6.89 (d, J=8.6 Hz, 1H), 6.99 (d, J=8.7
Hz, 1H), 7.07 (d, J=8.8 Hz, 1H), 7.15 (d, J=8.9 Hz,
1H), 7.20–7.27 (m, 5H), 7.33–7.38 (m, 2H), 7.40–7.48
(m, 4H), 7.57 (s, 1H), 7.62 (dd, J=11.5, 8.6 Hz, 1H),
7.69 (s, 1H), 7.79 (d, J=9.1 Hz, 1H), 7.92 (d, J=8.7
Hz, 1H). 13C NMR (CDCl3) l 14.05, 14.08, 22.62,
22.65, 29.18, 29.26, 29.29, 29.40, 29.47, 30.89, 31.81,
31.88, 35.88, 35.96, 117.60 (q, JC–F=313.5 Hz), assign-
ment of all peaks of 13C NMR was difficult owing to
the 13C–31P coupling and the overlapping of peaks;
31P{1H} NMR (CDCl3) l 28.9 (s). Anal. calcd for
C49H54F3O4PS: C, 71.17; H, 6.58. Found: C, 71.44; H,
6.72. [h]2D0 +30 (c 1.3, CHCl3).
A solution of (R)-2,2%-diethoxy-6,6%-dioctyl-1,1%-binaph-
thyl 3 in 5 mL of methylene chloride was added drop-
wise to a BBr3 solution (1.0 M, 6.0 mL, in methylene
chloride) at 0°C. The reaction mixture was stirred for
12 h, treated with water, and extracted with methylene
chloride. The extract was dried over anhydrous MgSO4
and the solvent was evaporated. The residue was chro-
matographed on silica gel (hexane/ethyl acetate=5/1)
to give 0.8 g (95% yield) of the titled compound as
1
colorless oil. H NMR (CDCl3) l 0.85 (t, J=7.1 Hz,
6H), 1.21–1.38 (m, 20H), 1.63–1.69 (m, 4H), 2.71 (t,
J=7.8 Hz, 4H), 4.97 (s, 2H), 7.07 (d, J=8.7 Hz, 2H),
7.15 (d, J=8.6 Hz, 2H), 7.33 (d, J=9.0 Hz, 2H), 7.65
(s, 2H), 7.88 (d, J=9.0 Hz, 2H). 13C NMR (CDCl3) l
14.03, 22.60, 29.20, 29.34, 29.44, 31.35, 31.84, 35.74,
110.85, 117.56, 124.11, 126.81, 128.94, 129.57, 130.72,
131.67, 138.58, 152.02. Anal. calcd for C36H46O2: C,
84.66; H, 9.08. Found: C, 84.41; H, 9.28. [h]2D0 –66 (c
1.4, CHCl3).
4.5. (R)-2-Diphenylphosphino-6,6%-dioctyl-2%-trifluoro-
methanesulfonyloxy-1,1%-binaphthyl 7
4.3. (R)-2,2%-Bis(trifluoromethanesulfonyloxy)-6,6%-
dioctyl-1,1%-binaphthyl 5
Trichlorosilane (0.36 mL, 3.6 mmol) was added drop-
wise to a solution of (R)-2-diphenylphosphinyl-6,6%-
dioctyl-2%-trifluoromethanesulfonyloxy-1,1%-binaphthyl 6
(1.1 g, 1.3 mmol), and triethylamine (0.61 mL, 4.4
mmol) in 10 mL of xylene. The reaction mixture was
heated with stirring at 100°C for 12 h. After cooling to
room temperature, the mixture was diluted with diethyl
ether and quenched with small amount of saturated
sodium bicarbonate. The resulting suspension was
filtered through Celite and the Celite was washed with
diethyl ether. The combined organic layer was dried
over anhydrous MgSO4 and the solvent was evapo-
rated. The residue was chromatographed on silica gel
(hexane/ethyl acetate=40/1) to give 1.0 g (93% yield) of
Trifluoromethanesulfonic anhydride (2.7 mL, 16.2
mmol) was added dropwise to a solution of (R)-6,6%-
dioctyl-1,1%-bi-2-naphthol 4 (3.5 g, 6.8 mmol) and pyri-
dine (1.6 mL, 20.4 mmol) in 15 mL of methylene
chloride at 0°C. After stirring at 0°C for 1 h, the
reaction mixture was concentrated under reduced pres-
sure. The residue was diluted with ethyl acetate and
washed with 5% hydrochloric acid, saturated sodium
bicarbonate, and saturated sodium chloride. The
organic layer was dried over anhydrous MgSO4 and the
solvent was evaporated. The residue was chro-
matographed on silica gel (hexane) to give 5.0 g (95%
1
1
yield) of the titled compound as colorless oil. H NMR
the titled compound as colorless oil. H NMR (CDCl3)
(CDCl3) l 0.87 (t, J=6.9 Hz, 6H), 1.21–1.39 (m, 20H),
1.54–1.72 (m, 4H), 2.76 (t, J=7.6 Hz, 4H), 7.16 (d,
J=8.8 Hz, 2H), 7.24 (d, J=8.7 Hz, 2H), 7.56 (d, J=9.1
Hz, 2H), 7.75 (s, 2H), 8.04 (d, J=9.1 Hz, 2H). 13C
NMR (CDCl3) l 14.01, 22.59, 29.16, 29.31, 29.37,
30.93, 31.79, 35.85, 118.10 (q, JC–F=319.9 Hz), 119.10,
123.29, 126.53, 126.57, 129.49, 131.16, 131.52, 132.54,
142.11, 144.74. Anal. calcd for C38H44F6O6S2: C, 58.90;
H, 5.72. Found: C, 58.79; H, 5.78. [h]2D0 −108 (c 1.3,
CHCl3).
l 0.84–0.88 (m, 6H), 1.23–1.32 (m, 20H), 1.62–1.73 (m,
4H), 2.68 (t, J=7.8 Hz, 2H), 2.71 (t, J=7.9 Hz, 2H),
6.81 (d, J=8.8 Hz, 1H), 6.90 (d, J=8.8 Hz, 1H),
6.98–7.01 (m, 2H), 7.05–7.17 (m, 5H), 7.22–7.29 (m,
5H), 7.39 (dd, J=8.8, 3.0 Hz, 1H), 7.47 (d, J=9.3 Hz,
1H), 7.64 (s, 1H), 7.67 (s, 1H), 7.84 (d, J=8.3 Hz, 1H),
7.95 (d, J=9.3 Hz, 1H). 13C NMR (CDCl3) l 14.06,
14.09, 22.62, 22.64, 29.19, 29.24, 29.32, 29.33, 29.42,
29.45, 31.04, 31.09, 31.82, 31.86, 35.85, 35.95, 118.00 (q,
J
C–F=319.9 Hz), assignment of all peaks of 13C NMR
was difficult owing to the 13C–31P coupling and the
overlapping of peaks; 31P{1H} NMR (CDCl3) l –12.07
(s). FAB MS m/z (M++H) calcd for C49H55F3O3PS:
811.36. Found: 811.39. [h]2D0 −11 (c 1.3, CHCl3).
4.4. (R)-2-Diphenylphosphinyl-6,6%-dioctyl-2%-trifluoro-
methanesulfonyloxy-1,1%-binaphthyl 6
A mixture of (R)-2,2%-bis(trifluoromethanesulfonyloxy)-
6,6%-dioctyl-1,1%-binaphthyl
5
(1.8 g, 2.4 mmol),
4.6. (R)-2-Diphenylphosphino-2%-(3,5-dimethyl-4-
methoxyphenyl)-6,6%-dioctyl-1,1%-binaphthyl 8
diphenylphosphine oxide (1.0 g, 4.7 mmol), Pd(OAc)2
(0.054 g, 0.24 mmol), 1,4-bis(diphenylphosphino)butane
(0.1 g, 0.24 mmol), and diisopropylethylamine (1.6 mL,
9.4 mmol) in 20 mL of DMSO was heated with stirring
at 130°C for 18 h. After cooling to room temperature,
the reaction mixture was concentrated under reduced
pressure. The residue was diluted with ethyl acetate and
washed with water, 5% hydrochloric acid, and satu-
rated sodium chloride, successively. The organic layer
A mixture of (R)-2-diphenylphosphino-6,6%-dioctyl-2%-
trifluoromethanesulfonyloxy-1,1%-binaphthyl 7 (0.45 g,
0.55 mmol), NiCl2(PPh3)2 (0.072 g, 0.11 mmol), and
3,5-dimethyl-4-methoxyphenylmagnesium bromide (0.6
M, 2 mL, in tetrahydrofuran) was refluxed for 24 h.
The mixture was quenched with saturated ammonium
chloride on an ice bath and was extracted with diethyl

330
J. W. Han, T. Hayashi / Tetrahedron: Asymmetry 13 (2002) 325–331
ether. The extract was dried over anhydrous MgSO4
and the solvent was evaporated. The residue was chro-
matographed on silica gel (hexane/ethyl acetate=30/1)
to give 0.35 g (80% yield) of the titled compound as
J=7.0 Hz, 3H), 0.97 (d, J=6.9 Hz, 3H), 1.21–1.30 (m,
8H), 1.92 (d, J=3.9 Hz, 1H), 1.97 (q, J=6.9 Hz, 2H),
2.53 (m, 1H), 4.58 (dd, J=5.4, 3.9 Hz, 1H), 5.30 (dd,
J=15.4, 7.4 Hz, 1H), 5.44 (dt, J=15.4, 6.9 Hz, 1H),
7.23–7.34 (m, 5H); 13C NMR (CDCl3) l 14.09, 14.82,
22.61, 28.74, 29.39, 31.70, 32.63, 43.76, 77.49, 126.54,
127.17, 127.94, 131.46, 132.20, 142.67. Anal. calcd for
C17H26O: C, 82.87; H, 10.64. Found: C, 82.94; H, 10.91.
[h]2D0 –12.6 (c 1.1, CHCl3) for 69% ee.
1
colorless oil. H NMR (CDCl3) l 0.85–0.90 (m, 6H),
1.20–1.33 (m, 20H), 1.64–1.69 (m, 4H), 1.83 (s, 6H),
2.69 (t, J=8.0 Hz, 2H), 2.73 (t, J=8.0 Hz, 2H), 3.60 (s,
3H), 6.61 (s, 2H), 6.66 (t, J=7.1 Hz, 2H), 6.74 (d,
J=8.7 Hz, 1H), 6.82 (dd, J=8.7, 1.6 Hz, 1H), 6.90 (t,
J=7.4 Hz, 2H), 7.01–7.23 (m, 8H), 7.37 (d, J=8.7 Hz,
1H), 7.57 (d, J=8.5 Hz, 1H), 7.60 (s, 1H), 7.64 (d,
J=8.6 Hz, 1H), 7.66 (s, 1H), 7.93 (d, J=8.6 Hz, 1H).
13C NMR (CDCl3) l 14.07, 14.10, 15.70, 22.64, 22.67,
29.23, 29.25, 29.29, 29.38, 29.48, 29.53, 31.19, 31.24,
31.91, 35.91, 35.94, 59.54, assignment of all peaks of
13C NMR was difficult owing to the 13C–31P coupling
and the overlapping of peaks; 31P{1H} NMR (CDCl3) l
–14.20 (s). FAB MS m/z (M++H) calcd for C57H66OP:
797.48. Found: 797.51. [h]2D0 +130 (c 0.3, CHCl3).
4.9. Oxidation of (1S,2R)-(E)-2-methyl-1-phenyl-3-
decen-1-ol 11c with KMnO4 and NaIO4
To
a solution of (1S,2R)-(E)-2-methyl-1-phenyl-3-
decen-1-ol 11c (125 mg, 0.51 mmol) in 14 mL of t-butyl
alcohol was added a solution of K2CO3 (213 mg, 1.54
mmol) in 10 mL of water. A solution of NaIO4 (883
mg, 4.13 mmol) and KMnO4 (108 mg, 0.69 mmol) in 10
mL of water was added and the resulting solution was
adjusted to pH 8.5 with 2N NaOH. After stirring for 24
h, t-butyl alcohol was evaporated. The residue was
acidified with concentrated HCl, and 10% aqueous
solution of NaHSO3 was added to destroy the MnO2.
The solution was made basic with 2N NaOH. The
mixture was extracted with diethyl ether and washed
with water. The extract was dried over anhydrous
MgSO4 and the solvent was evaporated. A solution of
the crude acid in diethyl ether was treated with diazo-
methane at 0°C for 1 h. Acetic acid was added to
quench excess diazomethane and the mixture was
extracted with diethyl ether. The extract was washed
with saturated aqueous sodium hydrogen carbonate,
and dried over anhydrous MgSO4. Evaporation of the
solvent followed by preparative TLC on silica gel (hex-
ane/ethyl acetate=4/1) gave 48 mg (48% yield)
of methyl (2S,3S)-3-hydroxy-2-methyl-3-phenylpro-
panoate18 12. [h]D20 −16.4 (c 1.0, CHCl3) for 69% ee.
4.7. Palladium-catalyzed asymmetric hydrosilylation of
1,3-dienes
The reaction conditions and results are summarized in
Tables 1 and 2. A typical procedure is given for the
preparation of 3-(trichlorosilyl)cyclohexene 10a (entry
2, Table 1). To a mixture of [PdCl(p-C3H5)]2 (0.9 mg,
0.0025 mmol), the n-octylated MOP ligand 8 (8.0 mg,
0.0100 mmol), and 1,3-cyclohexadiene (277 mg, 2.0
mmol) was added dropwise trichlorosilane (0.24 mL,
2.4 mmol) at 0°C. The reaction mixture was stirred in a
sealed tube at 0°C for 72 h, and then distilled (bulb-to-
bulb) under a reduced pressure (170°C/20 torr) to give
345 mg (80% yield) of 3-(trichlorosilyl)cyclohexene 10a.
1H NMR spectra for allylsilanes, 3-(trichlorosilyl)-
cyclohexene 10a and 3-(trichlorosilyl)cyclopentene 10b,
have been reported in Ref. 7c.
4.7.1. (Z)-4-(Trichlorosilyl)-2-decene 10c. 1H NMR
(CDCl3) l 0.88 (t, J=7.2 Hz, 3H), 1.24–1.34 (m, 8H),
1.45–1.53 (m, 1H), 1.66 (dd, J=6.9, 1.9 Hz, 3H),
1.78–1.81 (m, 1H), 2.53 (td, J=11.0, 2.1 Hz, 1H), 5.15
(tq, J=10.9, 1.9 Hz, 1H), 5.76 (dq, J=10.8, 6.9 Hz,
1H).
Acknowledgements
This work was supported by ‘Research for the Future’
Program, the Japan Society for the Promotion of Sci-
ence, and a Grant-in-Aid for Scientific Research, the
Ministry of Education, Japan.
4.7.2. (Z)-4-Phenyl-4-(trichlorosilyl)-2-butene 10d. H
NMR (CDCl3) l 1.74 (d, J=5.9 Hz, 3H), 3.94 (d,
J=9.8 Hz, 1H), 5.81–5.85 (m, 2H), 7.25–7.34 (m, 5H).
4.8. Reaction of (Z)-4-(trichlorosilyl)-2-decene 10c with
benzaldehyde in DMF
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