Asymmetric addition of allylic stannanes to aldehydes catalyzed by binap·Ag(I) complex

Article abstract of DOI:10.1246/bcsj.74.1129

Catalytic asymmetric allylation of aldehydes with allylic trialkylstannanes was achieved with BINAP·AgOTf complex as catalyst. The chiral silver(I) catalyst was readily prepared by stirring an equimolar mixture of BINAP and silver(I) triflate in TI-IF at

Full text of DOI:10.1246/bcsj.74.1129

c. Jpn.
© 2001 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 74, 1129—1137 (2001) 1129
e Chemical
ciety of Ja-
n
e Chemical
ciety of Ja-
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Asymmetric Addition of Allylic Stannanes to Aldehydes Catalyzed by
BINAP•Ag(I) Complex
Asymmetric Addition of Allylic Stannanes
A. Yanagisawa et al.
Akira Yanagisawa, Hiroshi Nakashima, Yoshinari Nakatsuka, Atsushi Ishiba, and
01
29
Hisashi Yamamoto*
37
Graduate School of Engineering, Nagoya University, CREST, Japan Science and Technology Corporation (JST),
Chikusa, Nagoya 464-8603
SJA8
09-2673
408
(Received November 29, 2000)
vember
00
01
Catalytic asymmetric allylation of aldehydes with allylic trialkylstannanes was achieved with BINAP•AgOTf com-
plex as catalyst. The chiral silver(I) catalyst was readily prepared by stirring an equimolar mixture of BINAP and sil-
ver(I) triflate in THF at room temperature. The allylation of a variety of aromatic and α,β-unsaturated aldehydes resulted
in high yields and remarkable enantioselectivities. Addition of γ-substituted allylstannanes such as 2-butenyltributyl-
stannane and trialkyl-2,4-pentadienylstannanes exclusively gave γ-adducts. High anti-selectivity was also obtained in
the reaction with 2-butenyltributylstannane, irrespective of the configuration at the double bond.
Asymmetric allylation of carbonyl compounds to prepare
optically active secondary homoallylic alcohols is a useful syn-
thetic method, since the products are easily transformed into
optically active β-hydroxy carbonyl compounds and various
other chiral compounds.1 Although many studies on the reac-
tion employing a stoichiometric amount of chiral Lewis acids
have been reported, there are few catalytic processes including
chiral (acyloxy)borane (CAB) complex2 or a binaphthol-de-
rived chiral titanium complex3 as a catalyst. Reported herein is
a new catalytic enantioselective allylation reaction of alde-
hydes with allylic trialkylstannanes using BINAP•silver(I)
complex as a catalyst (Eq. 1).4 High γ-, anti-, and enantiose-
lectivities are obtained by this method.
The BINAP•silver(I) catalyst was readily prepared by stir-
ring a 1:1 mixture of (S)-BINAP and silver(I) triflate in dry
THF at room temperature for 10 min. Treatment of benzalde-
hyde with an equimolar amount of allyltributylstannane in dry
THF in the presence of this catalyst (0.05 molar amount) at
ꢀ20 ˚C for 8 h furnished the (S)-enriched homoallylic alcohol
in 88% yield with 96% ee (Table 1, entry 4). Using a variety
Table 1.
Allylation Reaction of Benzaldehyde with
Allyltributylstannance in the Presence of Various Chiral
Phosphine–Silver(I) Complexa)
(1)
Results and Discussion
Enantioselective Allylation and Methallylation of Alde-
hydes. We have previously shown that highly chemoselec-
tive allylation of carbonyl compounds takes place with tetraal-
lylstannane in acidic aqueous solution.5 Our ongoing concern
about selective allylation has guided us to attempt an investiga-
tion of allylation of aldehydes with allyltributylstannane cata-
lyzed by various metal compounds under neutral reaction con-
ditions. Among the metal catalysts tested, silver(I) compound
showed remarkable reactivity. For example, treatment of ben-
zaldehyde with allyltributylstannane under the influence of
0.05 molar amount of silver(I) trifluoroacetate in a 1:1 mixture
of THF and H2O at 20 ˚C for 4 h gave the homoallylic alcohol
in 48% yield. Addition of 0.1 molar amount of triphenylphos-
phine raised the chemical yield to > 90%. This result led us to
use chiral phosphine•silver(I) complex as a catalyst for asym-
metric allylation of aldehydes with allylic stannanes.
Configu
ration
Entry
Chiral phosphine•AgX
Yield%b)
ee%c)
(S)-BINAP•AgOCOCF3
(S)-BINAP•AgClO4
1
2
3
4
5
6
7
47
1
26
88
97
4
40
26
53
96
2
S
S
S
(S)-BINAP•AgNO3
(S)-BINAP•AgOTf
S
(R,R)-CHIRAPHOS•AgOTf
(S,S)-Me-DUPHOS•AgOTf
(S,S)-Et-DUPHOS•AgOTf
R
R
R
48
3
13
a) Unless otherwise specified, the reaction was carried out
using chiral phophine•AgX (0.05 mol amt.), allyltributyl-
stannane (1 mol amt.) and benzaldehyde (1 mol amt.) in
THF at ꢀ20 ˚C for 8 h. b) Isolated yield. c) Determined by
HPLC analysis (Chiralcel OD-H, Daicel Chemical Indus-
tries, Ltd.).

1130 Bull. Chem. Soc. Jpn., 74, No. 6 (2001)
Asymmetric Addition of Allylic Stannanes
of chiral phosphine–silver(I) catalysts, we examined the enan-
tioselectivity of this process; Table 1 shows enantiomeric ex-
cesses and yields of the products obtained by the reaction with
0.05 molar amount of other chiral phosphine–silver(I) com-
plexes in THF at ꢀ20 ˚C. The allylation catalyzed by (S)-BI-
NAP•AgOTf was also performed at various temperatures. The
results are as follows (temperature, yield, enantioselectivity):
20 ˚C, 16% yield, 79% ee; 0 ˚C, 16% yield, 86% ee; ꢀ20 ˚C,
88% yield, 96% ee; ꢀ45 ˚C, 54% yield, 94% ee; ꢀ78 ˚C, <
1% yield. The catalyst was deactivated for prolonged periods
above 0 ˚C. As a consequence, the reaction catalyzed by the
BINAP•silver(I) triflate complex at ꢀ20 ˚C afforded the high-
est yield and ee.
hydes but also with α,β-unsaturated aldehydes (entries 2 and
5), except one aliphatic aldehyde, which gave a lower chemical
yield (entry 9); (2) In the reaction with α,β-unsaturated alde-
hydes, 1,2-addition reaction took place exclusively (entries 2
and 5); (3) the enantioselectivity was not affected by introduc-
tion of a methyl group into the ortho-position of benzaldehyde
(compare entries 1 and 6); (4) an electron-withdrawing substit-
uent at the para-position of benzaldehyde enhanced the allyla-
tion (compare entries 1, 7, and 8).
In order to elucidate the catalytic mechanism of the present
allylation and to determine whether the BINAP•Ag(I) complex
acts as a chiral Lewis acid catalyst or an allylsilver reagent, we
undertook an experiment which had the following result: when
(S)-BINAP•AgOTf complex was treated with an equimolar
amount of allyltributylstannane in THF at 20 ˚C, followed by
quenching half of the resulting reaction mixture with brine,
98% of the allylstannane compound was recovered. Exposure
of another half of the mixture to an equimolar amount of ben-
zaldehyde at ꢀ20 ˚C for 8 h gave the (S)-homoallylic alcohol
in 35% yield with > 99% ee. In this reaction, allyltributylstan-
nane was entirely consumed; however, ca. 50% of benzalde-
hyde remained unreacted, probably owing to unknown side re-
actions peculiar to this stoichiometric reaction system. This
result shows that no transmetallation occurs prior to addition
of benzaldehyde in this stoichiometric allylation.
Table 2 summarizes the data given by the reaction of diverse
aldehydes with equimolar amounts of allyltributylstannane at
ꢀ20 ˚C in THF. The chief features of the results are as fol-
lows: (1) all of the reactions were furnished in high yields and
remarkable enantioselectivities not only with aromatic alde-
Table 2. Asymmetric Allylation Reactions of Aldehydes
Catalyzed by BINAP•AgOTf Complexa)
We found that additions of 2-methyl-2-propenylstannanes6
to aldehydes also took place highly enantioselectively employ-
ing BINAP•AgOTf catalyst.4a,8 For instance, the 2-methyl-2-
propenylation of benzaldehyde by 0.05 molar amount of (R)-
BINAP•silver(I) triflate in THF at ꢀ20 ˚C for 8 h gave the cor-
responding optically active homoallylic alcohol in 75% yield
with 92% ee (Eq. 2). In general, reactivity of the 2-methyl-2-
propenylstannane was relatively lower than that of allyltribu-
tylstannane, while use of an increased amount (up to 0.2 molar
amount) of the catalyst resulted in satisfactory yields. The oth-
er features of this process were almost the same as those of the
allyl addition process.4a
Config
uration
Entry
Aldehyde
Yield%b)
ee%c)
1
2d)
88
83
96
88
S
S
3d)
89
97
S
S
4e)
5f)
94
72
93
93g)
6
7
85
59
97
97
(2)
S
γ
Asymmetric - and Antiselective 2-Butenylation of Alde-
hydes. Condensation of γ-substituted allylmetals with alde-
hydes is a fascinating subject with regard to the regioselectivi-
ties (α/γ) and stereoselectivities (E/Z or anti/syn). 2-Butenyl-
tributylstannane is well known to react with aldehydes in
CH2Cl2 γ- and syn(erythro)-selectively irrespective of the con-
figuration of the 2-butenylstannane in the presence of 2 molar
amounts of BF3•OEt2.9 If the BINAP•silver(I) complex be-
haves as a chiral Lewis acid catalyst, optically active γ-allylat-
ed syn-homoallylic alcohols should be predominantly pro-
duced in the 2-butenylation. Accordingly, we investigated the
BINAP•silver(I) catalyzed reaction of (E)- and (Z)-2-butenyl-
stannane.8 Addition of (E)-2-butenyltributylstannane (E/Z ꢁ
95/5) to benzaldehyde in the presence of 0.2 molar amount of
(R)-BINAP•AgOTf in THF at ꢀ20 ˚C–r.t., however, exclusive-
ly gave the γ-adduct with an anti/syn ratio of 85/15, against our
expectations.10 The anti-isomer was obtained in 94% ee with
8
95
47
96
88
9f)
a) Unless otherwise specified, the reaction was carried out
using (S)-BINAP•AgOTf (0.05 mol amt.), allyltributylstan-
nane (1 mol amt.) and aldehyde (1 mol amt.) in THF at
ꢀ20 ˚C for 8 h. b) Isolated yield. c) Determined by HPLC
analysis (Chiralcel OD-H, OJ, or Chiralpak AD, Daicel
Chemical Industries, Ltd.). d) 3 mol amt. of allyltributyl-
stannane and 0.15 mol amt. of (S)-BINAP•AgOTf was
used. e) 4 mol amt. of allyltributylstannane and 0.2 mol
amt. of (S)-BINAP•AgOTf was used. f) The reaction was
started using 2 mol amt. of allyltributylstannane and 0.1
mol amt. of (R)-BINAP•AgOTf, and 0.1 mol amt. of the
catalyst was added after 4 h. g) Determined by HPLC anal-
ysis (Chiralpak AD) of the benzoate of the product.

A. Yanagisawa et al.
Bull. Chem. Soc. Jpn., 74, No. 6 (2001) 1131
1R,2R configuration (Eq. 3). Use of (Z)-2-butenyltributylstan-
nane (E/Z ꢁ 2/98) or a nearly 1:1 mixture of (E)- and (Z)-2-
butenyltributylstannane resulted in a similar anti/syn ratio and
enantioselectivity (Eq. 3).
a catalyst.16
As described above, 2-butenyltributylstannane is proven to
react selectively at the γ-position with an aldehyde in the pres-
ence of a catalytic amount of BINAP•silver(I) complex.8 We
first studied the condensation of pentadienylstannanes with al-
dehydes using achiral phosphine–silver(I) catalysts in aqueous
media, with the expectation that such γ-substituted allylstan-
nanes should also show similar high γ-selectivity. When tribu-
tylpentadienylstannane was added to a mixture of equimolar
amount of benzaldehyde and 0.1 molar amount of bis(triphe-
nylphosphine)–silver(I) triflate in a 1:1 mixture of THF and
H2O at 20 ˚C for 3 h, the γ-adduct was obtained nearly exclu-
sively in 61% yield (Eq. 4).
(3)
γ
Asymmetric -selective Pentadienylation of Aldehydes.
Reaction of aldehydes with 2,4-pentadienylmetal compounds
yields two regioisomeric dienols, ε-adduct and γ-adduct,
which are both valuable synthetic intermediates of natural
products, and various regioselective processes of introducing a
pentadienyl group into organic compounds have been devel-
oped using diverse metal reagents (Fig. 1).11 The ε-attacked
conjugated dienols are selectively formed in the reaction of
pentadienylsilanes or stannanes with aldehydes promoted by
strong Lewis acid, such as BF3•OEt2 and TiCl4, via an acyclic
transition-state structure.12 In contrast, predominant formation
of the unconjugated γ-adducts via a cyclic transition-state
structure has been accomplished employing more reactive pen-
tadienylmetal compounds (M ꢁ Mg, Zn, B, etc.).13 However,
as far as we know, the asymmetric version of these reactions
has still not been achieved, probably because the γ-pentadieny-
lated products are not obtained by the Lewis acid-promoted re-
actions using silane and stannane reagents which are more
suitable to asymmetric induction.14 We achieved a novel cata-
lytic enantioselective γ-pentadienylation reaction of aldehydes
with pentadienylstannanes15 using BINAP•silver(I) complex as
(4)
This γ-allylation preference encouraged us to investigate the
BINAP•silver(I) complex-catalyzed pentadienylation under
anhydrous reaction conditions. When benzaldehyde was treat-
ed with tributylpentadienylstannane in dry THF under the in-
fluence of 0.1 molar amount of (S)-BINAP•AgOTf at ꢀ20 ˚C
for 8 h, the optically active γ-pentadienylated alcohol was pro-
duced in 61% yield with 90% ee (Table 3, entry 1). Table 3
Table 3.
Enantioselective Addition of Pentadienylstann-
anes to Aldehydes Catalyzed by BINAP•AgOTf Complexa)
Entrry
1d)
2
SnR1
Aldehyde
PhCHO
Yield%b) ee%c)
3
SnBu3
SnMe3
61
68
90
89
3
SnMe3
57
90
4
5
SnMe3
SnMe3
41
62
87
89
6
7
8
9
SnBu3
SnMe3
SnBu3
SnBu3
(E)-PhCHꢁCHCHO
73
68
52
58
58
71
—
PhCH2CH2CHO
PhCOCH3
< 1
a) Unless otherwise specified, the reaction was carried out
using (R)-BINAP•AgOTf (0.1 mol amt.), tributylpentadie-
nylstannane (R1 ꢁ n-Bu, E:Z ꢁ 97:3, 1 mol amt.) or trim-
ethylpentadienylstannane (R1 ꢁ Me, E:Z ꢁ 90:10, 1 mol
amt.), and aldehyde (1 equiv) in THF at ꢀ20 ˚C for 8 h. b)
Isolated yield. c) Determined by HPLC analysis (Chiralcel
OD-H or Chiralpak AD, Daicel Chemical Industries, Ltd.).
d) (S)-BINAP•AgOTf was used.
Fig. 1.
hydes.
Reaction of Pentadinylmetal reagents with alde-

1132 Bull. Chem. Soc. Jpn., 74, No. 6 (2001)
Asymmetric Addition of Allylic Stannanes
shows other results acquired in the reaction of various alde-
hydes and pentadienylstannanes catalyzed by (R)-BINAP•Ag-
OTf. Several key findings are as follows: (1) no meaningful
differences in chemical yield or enantioselectivity were seen
between tributylpentadienylstannane and trimethylpentadie-
nylstannane (compare entries 1, 2, 6, and 7); (2) substituted ar-
omatic aldehydes and furfural exhibited comparable enantiose-
lectivity to that of benzaldehyde (entries 3–5); (3) exclusive
1,2-selectivity was observed for the reaction of an α,β-unsatur-
ated aldehyde (entries 6 and 7); (4) ketone showed no reactivi-
ty under the standard reaction conditions (entry 9).
It is not clear why anti selectivity is obtained for the 2-bute-
nyl addition reaction (Eq. 3) regardless of the double-bond ge-
ometry of the stannane, although some transition-state models
are conceivable (Fig. 2). (E)- and (Z)-2-Butenyltributylstan-
nane have been reported to react with aldehydes in CH2Cl2
with γ- and syn(erythro)-selectivities in the presence of 2 mo-
lar amounts of BF3•OEt2. For the syn-selective reaction of 2-
butenylstannane, Y. Yamamoto proposed an acyclic anti-
periplanar transition-state structure A.9 Subsequently, Keck et
al. suggested a syn-synclinal alternative B to explain the higher
syn-selectivity obtained with the E-stannane.17 If the BI-
NAP•Ag(I) complex acts as a Lewis acid in the anti-selective
allylation, the reaction might proceed via an acyclic anti-
periplanar D, which seems to have the least steric interaction
between BINAP•Ag(I) and the stannyl methylene carbon and/
or the R1 group of the allylic stannane. A cyclic transition-
state E is also a possible model for a Lewis acid mechanism,
since pentadienylstannanes react selectively at the γ-carbon, as
shown in Table 3. Nishigaichi and Takuwa proposed a similar
cyclic model for ZnCl2-promoted anti-selective γ-allylation of
aldehydes with γ-substituted allylstannanes.10a In contrast, a
cyclic transition-state model G containing a BINAP-coordinat-
ed silver atom instead of trialkylstannyl group is a probable al-
ternative leading to the anti-product when transmetallation to
an allylic silver occurs and E/Z isomerization of the silver
compound is sufficiently rapid. The corresponding syn-ho-
moallylic alcohol should be obtained from the (Z)-allylic silver
via a cyclic transition-state model F. It is uncertain whether
the BINAP•Ag(I) catalyzed allylation advances by the Lewis
acid mechanism or the transmetallation mechanism. The result
that almost no transmetallation took place at all before addition
of aldehyde, as described above, supports the Lewis acid
mechanism. However, the transmetallation pathway cannot be
denied completely because the recovered 2-butenyltributyl-
stannane was a little isomerized: for instance, reaction of
equimolar amount of (Z)-2-butenyltributylstannane (E/Z ꢁ 7/
93) with benzaldehyde in the presence of 0.2 molar amount of
(R)-BINAP•AgOTf in THF at ꢀ20–20 ˚C for 24 h gave a 14/
86 mixture of (E)- and (Z)-2-butenylstannane in 47% recov-
ered yield and a mixture of homoallylic alcohols in 30% com-
bined yield with an anti/syn ratio of 86/14. The enantioselec-
tivities of the anti- and syn-isomers were 94% ee and 65% ee,
respectively. Single electron transfer (SET) mechanism is also
a conceivable alternative; however, at present we have no ex-
perimental evidence for the mechanism.
Conclusion
We have described here a novel method for highly enanti-
oselective allylation of aldehydes with allylic trialkylstannanes
using a catalytic amount of BINAP•Ag(I) complex. The main
features of the present process are as follows: (1) the procedure
is operationally simple and can furnish a variety of optically
active homoallylic alcohols with high enantioselectivity; (2) γ-
adducts are exclusively formed in the reaction with 2-butenyl-
and 2,4-pentadienylstannanes; (3) remarkable anti-selectivity
is observed for the reaction with 2-butenyltributylstannanes, ir-
respective of the configuration at the double bond. The reac-
tion represents a new class of asymmetric allylation catalyzed
by chiral transition metal compounds and can be performed on
a substantial scale using ordinary laboratory equipment, be-
cause no complex preparation of catalyst is required. The re-
Fig. 2.
Probable acyclic and cyclic transition state structures.

A. Yanagisawa et al.
Bull. Chem. Soc. Jpn., 74, No. 6 (2001) 1133
chromatography on silica gel (1:10 ethyl acetate/hexane as the
eluant) to afford the homoallylic alcohol (258 mg, 88% yield) as a
colorless oil. The enantioselectivity was determined to be 96% ee
by HPLC analysis using a chiral column (Chiralcel OD-H, Daicel
Chemical Industries, Ltd., hexane/i-PrOH ꢁ 20/1, flow rate ꢁ 0.5
mL/min): tminor ꢁ 18.2 min (R), tmajor ꢁ 19.9 min (S). The abso-
lute configuration was determined to be S by comparison of the
[α]D value with reported data; (R)-enriched alcohol (90% ee): [α]D
ꢃ43.7˚ (c 6.7, benzene).21 Observed [α]D value of the product
with 96% ee: [α]2D6 ꢀ50.5˚ (c 1.1, benzene). Spectral data of the
product: TLC Rf 0.34 (1:3 ethyl acetate/hexane); IR (neat) 3700–
3120, 3077, 3031, 2907, 1642, 1603, 1493, 1455, 1316, 1198,
1115, 1076, 1048, 916, 870, 758, 700 cmꢀ1; 1H NMR (300 MHz,
CDCl3) δ 2.01 (d, 1 H, J ꢁ 2.5 Hz, OH), 2.52 (m, 2 H, CH2), 4.75
(dt, 1 H, J ꢁ 6.9, 2.5 Hz, CH), 5.14–5.20 (m, 2 H, 2 vinyls), 5.82
(m, 1 H, vinyl), 7.25–7.37 (m, 5 H, aromatic); 13C NMR (75 MHz,
CDCl3) δ 43.5, 73.2, 117.8, 125.7 (2 C), 127.2, 128.1 (2 C), 134.3,
143.8.
markable regio- and stereoselectivities of the allylation reac-
tion provide an unprecedented route to homoallylic alcohols;
the route is widely applicable to organic synthesis.
Experimental
General. Analytical TLC was done on E. Merck precoated
(0.25 mm) silica gel 60 F254 plates. Column chromatography was
conducted using silica gel 60 (E. Merck 9385, 230–400 mesh).
Infrared (IR) spectra were recorded on a Shimadzu FTIR-8100
spectrometer. 1H NMR spectra were measured on a Varian Gemi-
1
ni-300 (300 MHz) spectrometer. Chemical shifts of H NMR
spectra were reported relative to tetramethylsilane (δ 0) or chloro-
form (δ 7.26). Splitting patterns are indicated as s, singlet; d, dou-
blet; t, triplet; q, quartet; m, multiplet; br, broad. 13C NMR spectra
were measured on a Varian Gemini-300 (75 MHz) spectrometer.
Chemical shifts of 13C NMR spectra were reported relative to
CDCl3 (δ 77.0). Analytical gas-liquid phase chromatography
(GC) was performed on a Shimadzu GC-8A instrument equipped
with a flame ionization detector and a capillary column of PEG-
HT (0.25 ꢂ 25000 mm), using nitrogen as carrier gas. Analytical
high-performance liquid chromatography (HPLC) was done with
a Shimadzu 10A instrument using a chiral column (4.6 mm ꢂ 25
cm, Daicel CHIRALCEL OB-H, OD-H, OJ, or CHIRALPAK
AD). Optical rotation was measured on a JASCO DIP-1000 pola-
rimeter. Microanalyses were accomplished at the Faculty of Agri-
culture, Nagoya University.
(S),(E)-1-Phenyl-1,5-hexadien-3-ol (Entry 2 in Table 2).20
TLC Rf 0.28 (1:3 ethyl acetate/hexane); IR (neat) 3670–3120,
3079, 3026, 2979, 1642, 1599, 1579, 1493, 1449, 1130, 1071,
1
1030, 967, 916, 749, 693 cmꢀ1; H NMR (300 MHz, CDCl3) δ
1.78 (br, 1 H, OH), 2.39 (m, 2 H, CH2), 4.37 (dd, 1 H, J ꢁ 12.3,
6.1 Hz, CH2), 5.16–5.22 (m, 2 H, 2 vinyls), 5.87 (m, 1 H, vinyl),
6.25 (dd, 1 H, J ꢁ 15.9, 6.3 Hz, vinyl), 6.62 (d, 1 H, J ꢁ 15.7 Hz,
vinyl), 7.22–7.40 (m, 5 H, aromatic); 13C NMR (75 MHz, CDCl3)
δ 41.9, 71.7, 118.4, 126.4 (2 C), 127.6, 128.5 (2 C), 130.3, 131.5,
134.0, 136.6; [α]2D4 ꢃ15.4˚ (c 1.1, Et2O). The enantioselectivity
was determined to be 88% ee by HPLC analysis using a chiral col-
umn (Chiralcel OD-H, Daicel Chemical Industries, Ltd., hexane/i-
PrOH ꢁ 20/1, flow rate ꢁ 1.0 mL/min): tminor ꢁ 13.3 min (R), tma-
jor ꢁ 23.5 min (S).
All experiments were carried out under an atmosphere of stan-
dard grade argon gas (oxygen < 10 ppm) and exclusion of direct
light. Dry THF was used as purchased from Wako Pure Chemical
(dehydrated, > 99.5%, water: < 0.005%). Silver triflate (99ꢃ%)
was used as purchased from Aldrich. (R)- and (S)-BINAP (guar-
anteed reagent) were used as purchased from Nacalai Tesque. Al-
lyltributylstannane (Aldrich) and aldehydes were purified by dis-
tillation before use. Tributyl(2-methyl-2-propenyl)stannane, (E)-
enriched 2-butenyltributylstannane (E/Z ꢁ 95/5), and (Z)-enriched
2-butenyltributylstannane (E/Z ꢁ 2/98) were synthesized from the
corresponding allylic chlorides by reaction with tributylstannyl-
lithium in dry THF18 and were purified by distillation before use.
(E)- and (Z)-enriched 2-butenyl chlorides were prepared by treat-
ment of the corresponding allylic alcohols with a mixture of N-
chlorosuccinimide, and dimethyl sulfide in CH2Cl2.19 Pentadie-
nylstannanes were prepared by reaction of a pentadienyl Grignard
reagent, generated from 1-chloro-2,4-pentadiene and magnesium
turnings, with R3SnCl in ether, for R ꢁ n-Bu, E:Z ꢁ 97:3; for R
ꢁ Me, E:Z ꢁ 90:10.15 Other chemicals were used as purchased.
Typical Experimental Procedure for Asymmetric Allylation
of Aldehydes with Allylic Tributylstannane Reagents Cata-
lyzed by BINAP•AgOTf Complex: Synthesis of (S)-1-Phenyl-
(S)-1-(1-Naphthyl)-3-buten-1-ol (Entry 3 in Table 2).21,22
TLC Rf 0.36 (1:3 ethyl acetate/hexane); IR (neat) 3650–3120,
3071, 2979, 2940, 2908, 1640, 1597, 1510, 1433, 1395, 1167,
1055, 916, 801, 777 cmꢀ1; 1H NMR (300 MHz, CDCl3) δ 2.16 (d,
1 H, J ꢁ 2.8 Hz, OH), 2.57–2.72 (m, 1 H, one proton of CH2),
2.72–2.85 (m, 1 H, one proton of CH2), 5.17–5.27 (m, 2 H, 2 vi-
nyls), 5.54 (m, 1 H, CH), 5.94 (m, 1 H, vinyl), 7.46–7.55 (m, 3 H,
aromatic), 7.67 (d, 1 H, J ꢁ 7.1 Hz, aromatic), 7.79 (d, 1 H, J ꢁ
8.2 Hz, aromatic), 7.87–7.90 (m, 1 H, aromatic), 8.08 (d, 1 H, J ꢁ
7.8 Hz, aromatic); 13C NMR (75 MHz, CDCl3) δ 42.7, 69.8,
118.0, 122.7, 122.9, 125.3 (2 C), 125.9, 127.8, 128.8, 130.1,
133.6, 134.7, 139.4; [α]2D5ꢀ96.0˚ (c 1.1, benzene). The enantiose-
lectivity was determined to be 97% ee by HPLC analysis using a
chiral column (Chiralcel OD-H, Daicel Chemical Industries, Ltd.,
hexane/i-PrOH ꢁ 9/1, flow rate ꢁ 1.0 mL/min): tmajor ꢁ 7.8 min
(S), tminor ꢁ 12.8 min (R).
(S)-1-(2-Furyl)-3-buten-1-ol (Entry 4 in Table 2).23 TLC Rf
0.30 (1:3 ethyl acetate/hexane); IR (neat) 3750–3040, 3079, 2980,
1644, 1505, 1436, 1341, 1229, 1150, 1057, 1011, 922, 885, 864,
812, 739 cmꢀ1; 1H NMR (300 MHz, CDCl3) δ 2.00 (br, 1 H, OH),
2.61–2.66 (m, 2 H, CH2), 4.76 (m, 1 H, CH), 5.14–5.23 (m, 2 H, 2
vinyls), 5.82 (m, 1 H, vinyl), 6.26 (d, 1 H, J ꢁ 3.2 Hz, vinyl), 6.34
(dd, 1 H, J ꢁ 3.1, 1.6 Hz, vinyl), 7.39 (d, 1 H, J ꢁ 1.8 Hz, vinyl);
13C NMR (75 MHz, CDCl3) δ 40.0, 66.8, 106.0, 110.0, 118.4,
133.6, 141.9, 155.9; [α]2D3ꢀ27.2˚ (c 1.1, Et2O). The enantioselec-
tivity was determined to be 93% ee by HPLC analysis using a
chiral column (Chiralcel OB-H, Daicel Chemical Industries, Ltd.,
hexane/i-PrOH ꢁ 20/1, flow rate ꢁ 0.5 mL/min): tminor ꢁ 17.5
min (R), tmajor ꢁ 18.7 min (S).
3-buten-1-ol (Entry 4 in Table 1 and Entry 1 in Table 2).20
A
mixture of AgOTf (26.4 mg, 0.103 mmol) and (S)-BINAP (66.5
mg, 0.107 mmol) was dissolved in dry THF (3 mL) under argon
atmosphere and with direct light excluded, and stirred at 20 ˚C for
10 min. To the resulting solution was added dropwise a THF solu-
tion (3 mL) of benzaldehyde (208 mg, 1.96 mmol) and allyltribu-
tylstannane (663 mg, 2.00 mmol) successively at ꢀ20 ˚C. The
mixture was stirred for 8 h at this temperature and treated with a
mixture of 1 M (ꢁ1 mol dmꢀ3) HCl (10 mL) and solid KF (ca. 1
g) at ambient temperature for 30 min. The resulting precipitate
was filtered off by a glass filter funnel filled with Celite® and silica
gel. The filtrate was dried over MgSO4 and concentrated in vacuo
after filtration. The residual crude product was purified by column
(E)-1,5-Nonadien-4-ol (Entry 5 in Table 2).24 TLC Rf 0.40

1134 Bull. Chem. Soc. Jpn., 74, No. 6 (2001)
Asymmetric Addition of Allylic Stannanes
(1:3 ethyl acetate/hexane); IR (neat) 3700–3110, 3079, 2961,
(1:5 ethyl acetate/hexane); IR (neat) 3630–3130, 3031, 1647,
2930, 2874, 1671, 1642, 1457, 1437, 1379, 1315, 1032, 968, 914
1602, 1495, 1455, 1375, 1200, 1055, 1026, 891, 756, 700 cmꢀ1
;
1
cmꢀ1; H NMR (300 MHz, CDCl3) δ 0.90 (s, 3 H, J ꢁ 7.3 Hz,
1H NMR (300 MHz, CDCl3) δ 1.81 (s, 3 H, CH3), 2.11 (d, 1 H, J
ꢁ 2.2 Hz, OH), 2.44 (d, 2 H, J ꢁ 6.9 Hz, CH2), 4.83 (dt, 1 H, J ꢁ
6.9, 2.1 Hz, CH), 4.87 (s, 1 H, vinyl), 4.94 (s, 1 H, vinyl), 7.25–
7.41 (m, 5 H, aromatic); [α]2D3ꢃ55.3˚ (c 1.3, benzene). The enan-
tioselectivity was determined to be 92% ee by HPLC analysis us-
ing a chiral column (Chiralcel OD-H, Daicel Chemical Industries,
CH3), 1.40 (m, 2 H, CH2), 1.61 (br, 1 H, OH), 2.02 (dd, 2 H, J ꢁ
14.0, 7.3 Hz, CH2), 2.29 (m, 2 H, CH2), 4.13 (m, 1 H, CH), 5.11–
5.17 (m, 2 H, 2 vinyls), 5.45–5.53 (m, 1 H, vinyl), 5.63–5.80 (m, 2
H, 2 vinyls); [α]2D3ꢀ1.2˚ (c 1.0, Et2O). The enantioselectivity was
determined to be 93% ee by HPLC analysis of the benzoate of the
product using a chiral column (Chiralpak AD, Daicel Chemical
Industries, Ltd., hexane/i-PrOH ꢁ 400/1, flow rate ꢁ 0.5 mL/
min): tmajor ꢁ 13.3 min, tminor ꢁ 15.5 min.
Ltd., hexane/i-PrOH ꢁ 20/1, flow rate ꢁ 0.5 mL/min): tminor
16.2 min (S), tmajor ꢁ 17.9 min (R).
ꢁ
Typical Experimental Procedure for Asymmetric 2-Buteny-
lation of Benzaldehyde with 2-Butenyltributylstannane Cata-
lyzed by BINAP•AgOTf Complex: Synthesis of (1R,2R)-2-Me-
thyl-1-phenyl-3-buten-1-ol (Eq. 3).29 A mixture of AgOTf (26
mg, 0.10 mmol) and (R)-BINAP (62 mg, 0.10 mmol) was dis-
solved in dry THF (3 mL) under argon atmosphere and exclusion
of direct light, and stirred at 20 ˚C for 10 min. To the resulting so-
lution was added a THF solution (3 mL) of benzaldehyde (53 mg,
0.50 mmol) and then (E)-2-butenyltributylstannane (E/Z ꢁ 95/5,
690 mg, 2.0 mmol) was added dropwise at ꢀ20 ˚C. The mixture
was stirred for 8 h at this temperature and then for 16 h at 20 ˚C,
and treated with a mixture of 1 M HCl (10 mL) and solid KF (ca. 1
g) at ambient temperature for 30 min. After the resulting precipi-
tate was filtered off, the organic layer was separated, washed with
a saturated aqueous NaHCO3 solution and brine, dried over anhy-
drous MgSO4, and concentrated in vacuo after filtration. The re-
sidual crude product was purified by column chromatography on
silica gel to afford a mixture of homoallylic alcohols (46 mg, 56%
yield as a colorless oil): the α/γ and anti/syn ratios were deter-
mined to be < 1/99 and 85/15, respectively, by GC analysis. The
enantioselectivities of the anti- and syn-isomers were determined
to be 94% ee and 64% ee, respectively, by HPLC analysis using a
chiral column (Chiralcel OD-H, Daicel Chemical Industries, Ltd.,
hexane/i-PrOH ꢁ 40/1, flow rate ꢁ 0.5 mL/min): tanti-minor ꢁ 15.0
min (1S,2S), tsyn-minor ꢁ 15.5 min (1S,2R), tanti-major ꢃ syn-major ꢁ 17.8
min (1R,2R ꢃ 1R,2S). The absolute configuration of the major
anti-isomer was determined to be 1R,2R by comparison of the
[α]D value with reported data. (1S,2S)-enriched alcohol (66% ee):
[α]D25 ꢀ73.4˚ (c 2.0, CHCl3).29 (1S,2R)-isomer (55% ee): [α]D25
ꢀ15.0˚ (c 0.93, CHCl3).29 Observed [α]D value of the product:
[α]3D0 ꢃ77.5˚ (c 0.8, CHCl3; data obtained on an 85:15 mixture of
anti- and syn-isomers). The absolute configuration of the major
syn isomer was determined to be 1R,2S by HPLC analysis.30
Spectral data obtained on an 85:15 mixture of anti and syn iso-
mers: TLC Rf 0.38 (1:5 ethyl acetate/hexane); IR (neat) 3630–
3130, 3081, 3065, 3031, 2977, 2932, 2872, 1640, 1603, 1495,
1-(o-Tolyl)-3-buten-1-ol (Entry 6 in Table 2).20b,25 TLC Rf
0.40 (1:3 ethyl acetate/hexane); IR (neat) 3650–3125, 3075, 3025,
2979, 1640, 1489, 1462, 1051, 916, 870, 756, 725 cmꢀ1; 1H NMR
(300 MHz, CDCl3) δ 1.94 (d, 1 H, J ꢁ 2.5 Hz, OH), 2.36 (s, 3 H,
CH3), 2.47 (m, 2 H, CH2), 4.99 (m, 1 H, CH), 5.16–5.23 (m, 2 H, 2
vinyls), 5.88 (m, 1 H, vinyl), 7.13–7.27 (m, 3 H, aromatic), 7.50
(d, 1 H, J ꢁ 7.4 Hz, aromatic); [α]2D6ꢀ83.8˚ (c 1.0, benzene). The
enantioselectivity was determined to be 97% ee by HPLC analysis
using a chiral column (Chiralcel OD-H, Daicel Chemical Indus-
tries, Ltd., hexane/i-PrOH ꢁ 20/1, flow rate ꢁ 0.5 mL/min): tminor
ꢁ 13.5 min, tmajor ꢁ 15.2 min.
(S)-1-(p-Methoxyphenyl)-3-buten-1-ol (Entry 7 in Table
2).20b,22 TLC Rf 0.27 (1:3 ethyl acetate/hexane); IR (neat) 3700–
3120, 3075, 3002, 2936, 2900, 2838, 1642, 1613, 1586, 1514,
1464, 1443, 1302, 1248, 1175, 1036, 1003, 918, 872, 833, 812,
770 cmꢀ1; 1H NMR (300 MHz, CDCl3) δ 1.94 (d, 1 H, J ꢁ 0.9 Hz,
OH), 2.50 (d, 2 H, J ꢁ 6.6 Hz, CH2), 3.81 (s, 3 H, CH3), 4.69 (t, 1
H, J ꢁ 6.3 Hz, CH), 5.11–5.18 (m, 2 H, 2 vinyls), 5.80 (m, 1 H,
vinyl), 6.89 (d, 2 H, J ꢁ 8.8 Hz, aromatic), 7.29 (d, 2 H, J ꢁ 8.8
Hz, aromatic); 13C NMR (75 MHz, CDCl3) δ 43.7, 55.2, 72.9,
113.7 (2 C), 118.1, 127.0 (2 C), 134.6, 136.0, 158.9; [α]2D5 ꢀ40.7˚
(c 1.1, benzene). The enantioselectivity was determined to be
97% ee by HPLC analysis using a chiral column (Chiralcel OD-H,
Daicel Chemical Industries, Ltd., hexane/i-PrOH ꢁ 20/1, flow
rate ꢁ 0.5 mL/min): tminor ꢁ 11.1 min (R), tmajor ꢁ 12.9 min (S).
1-(p-Bromophenyl)-3-buten-1-ol (Entry 8 in Table 2).26
TLC Rf 0.39 (1:3 ethyl acetate/hexane); IR (neat) 3680–3120,
3079, 2979, 2934, 2905, 1642, 1593, 1489, 1431, 1406, 1297,
1
1194, 1071, 1011, 918, 870, 826, 777, 739, 718 cmꢀ1; H NMR
(300 MHz, CDCl3) δ 2.03 (d, 1 H, J ꢁ 3.0 Hz, OH), 2.48 (m, 2 H,
CH2), 4.71 (m, 1 H, CH), 5.14–5.20 (m, 2 H, 2 vinyls), 5.80 (m, 1
H, vinyl), 7.24 (d, 2 H, J ꢁ 8.3 Hz, aromatic), 7.48 (d, 2 H, J ꢁ
8.3 Hz, aromatic); 13C NMR (75 MHz, CDCl3) δ 43.6, 72.5,
118.6, 121.1, 127.5 (2 C), 131.3 (2 C), 133.9, 142.7; [α]2D3 ꢀ26.1˚
(c 1.1, benzene). The enantioselectivity was determined to be
96% ee by HPLC analysis using a chiral column (Chiralcel OJ,
Daicel Chemical Industries, Ltd., hexane/i-PrOH ꢁ 9/1, flow rate
ꢁ 0.5 mL/min): tmajor ꢁ 15.7 min, tminor ꢁ 16.9 min.
1
1455, 1374, 1196, 1117, 1076, 1021, 914, 762, 702 cmꢀ1; H
NMR (300 MHz, CDCl3, anti isomer) δ 0.87 (d, 3 H, J ꢁ 6.9 Hz,
CH3), 2.16 (d, 1 H, J ꢁ 2.7 Hz, OH), 2.48 (m, 1 H, CH), 4.36 (dd,
1 H, J ꢁ 8.1, 2.4 Hz, CH), 5.17–5.24 (m, 2 H, 2 vinyls), 5.75–5.87
(m, 1 H, vinyl), 7.26–7.36 (m, 5 H, aromatic); 13C NMR (75 MHz,
CDCl3, anti isomer) δ 16.5, 46.3, 77.8, 116.9, 126.8 (2 C), 127.6,
128.2 (2 C), 140.6, 142.4.
Typical Experimental Procedure for Asymmetric Pentadie-
nylation of Aldehydes with (E)-Trialkyl-2,4-pentadienylstan-
nanes Catalyzed by BINAP•AgOTf Complex: Synthesis of 1-
Phenyl-2-vinyl-3-buten-1-ol (Entry 2 in Table 3).13i A mixture
of AgOTf (26 mg, 0.10 mmol) and (R)-BINAP (62 mg, 0.10
mmol) was dissolved in dry THF (4 mL) under argon atmosphere
and with exclusion of direct light, and stirred at 20 ˚C for 10 min.
To the resulting solution was added benzaldehyde (100 µL, 0.98
mmol) and then trimethylpentadienylstannane (E/Z ꢁ 90/10, 229
1-Phenyl-5-hexen-3-ol (Entry 9 in Table 2).22,25a,27 TLC Rf
0.33 (1:3 ethyl acetate/hexane); IR (neat) 3700–3120, 3027, 2930,
2863, 1642, 1603, 1497, 1455, 1075, 1049, 1040, 995, 916, 747,
700 cmꢀ1; 1H NMR (300 MHz, CDCl3) δ 1.60 (d, 1 H, J ꢁ 1.9 Hz,
OH), 1.80 (m, 2 H, CH2), 2.16–2.23 (m, 1 H, one proton of CH2),
2.29–2.36 (m, 1 H, one proton of CH2), 2.64–2.84 (m, 2 H, CH2),
3.68 (m, 1 H, CH), 5.15 (d, 2 H, J ꢁ 11.8 Hz, 2 vinyls), 5.75–5.86
(s, 1 H, vinyl), 7.16–7.31 (m, 5 H, aromatic); [α]2D3 ꢃ25.3˚ (c 1.0,
benzene). The enantioselectivity was determined to be 88% ee by
HPLC analysis using a chiral column (Chiralcel OD-H, Daicel
Chemical Industries, Ltd., hexane/i-PrOH ꢁ 20/1, flow rate ꢁ 0.5
mL/min): tminor ꢁ 17.3 min, tmajor ꢁ 25.3 min.
(R)-3-Methy-1-phenyl-3-buten-1-ol (Eq. 2).28 TLC Rf 0.33

A. Yanagisawa et al.
Bull. Chem. Soc. Jpn., 74, No. 6 (2001) 1135
mg, 0.99 mmol) was added over a period of 4 h with a syringe
pump at ꢀ20 ˚C. After being stirred for 4 h at this temperature,
the mixture was treated with a mixture of 1 M HCl (3 mL) and
solid KF (ca. 1 g) at ambient temperature for 30 min. After the re-
sulting precipitate was filtered off by a glass filter funnel filled
with Celite® and silica gel, the filtrate was dried over anhydrous
MgSO4 and concentrated in vacuo after filtration. The residual
crude product was purified by column chromatography on silica
gel to afford the γ-pentadienylated alcohol (116.5 mg, 68% yield)
as a colorless oil: TLC Rf 0.33 (1:5 ethyl acetate/hexane); IR
(neat) 3625–3130, 3081, 3031, 2980, 2880, 1636, 1605, 1495,
1-(2-Furyl)-2-vinyl-3-buten-1-ol (Entry 5 in Table 3). TLC
Rf 0.21 (1:5 ethyl acetate/hexane); IR (neat) 3710–3170, 3081,
1
2980, 2890, 1636, 1505, 1150, 1011, 922 cmꢀ1; H NMR (300
MHz, CDCl3) δ 2.22 (d, 1 H, J ꢁ 5.2 Hz, OH), 3.31 (dd, 1 H, J ꢁ
7.4, 15.1 Hz, CH), 4.62 (dd, 1 H, J ꢁ 4.9, 7.1 Hz, CH), 5.10 (d, 1
H, J ꢁ 12.1 Hz, vinyl), 5.11 (d, 1 H, J ꢁ 15.9 Hz, vinyl), 5.22 (d,
1 H, J ꢁ 18.7 Hz, vinyl), 5.24 (d, 1 H, J ꢁ 9.3 Hz, vinyl), 5.68–
5.90 (m, 2 H, J ꢁ 7.1, 10.4, 17.2 Hz, vinyl), 6.26 (d, 1 H, J ꢁ 3.3
Hz, vinyl), 6.33 (dd, 1 H, J ꢁ 1.9, 3.3 Hz, vinyl), 7.38 (dd, 1 H, J
ꢁ 0.8, 1.9 Hz, vinyl); 13C NMR (75 MHz, CDCl3) δ 53.7, 69.9,
107.7, 110.2, 117.6, 118.5, 136.2, 136.6, 142.2, 154.5. Found: C,
73.00; H, 7.65%. Calcd for C10H12O2: C, 73.15; H, 7.37%. The γ/
1
1455, 1416, 1194, 1040, 999, 918 cmꢀ1; H NMR (300 MHz,
1
CDCl3) δ 2.19 (d, 1 H, J ꢁ 3.2 Hz, OH), 3.11 (dt, 1 H, J ꢁ 7.1,
15.0 Hz, CH), 4.59 (dd, 1 H, J ꢁ 3.1, 7.0 Hz, CH), 5.01 (d, 1 H, J
ꢁ 17.9 Hz, vinyl), 5.05 (d, 1 H, J ꢁ 10.4 Hz, vinyl), 5.19 (d, 1 H,
J ꢁ 17.1 Hz, vinyl), 5.25 (d, 1 H, J ꢁ 10.4 Hz, vinyl), 5.68 (ddd, 1
H, J ꢁ 7.1, 10.4, 17.2 Hz, vinyl), 5.83 (ddd, 1 H, J ꢁ 8.2, 10.4,
18.2 Hz, vinyl), 7.25–7.38 (m, 5 H, aromatic); [α]2D9ꢃ60.8˚ (c 1.1,
CHCl3). The IR and 1H NMR spectral data indicated good agree-
ment with reported data.13i The γ/ε ratio was determined to be >
99/1 by 1H NMR analysis. The enantioselectivity of the γ-product
was determined to be 89% ee by HPLC analysis using a chiral col-
umn (Chiralcel OD-H, Daicel Chemical Industries, Ltd., hexane/i-
PrOH ꢁ 20/1, flow rate ꢁ 0.5 mL/min): tminor ꢁ 18.7 min, tmajor ꢁ
22.5 min.
1-(o-Tolyl)-2-vinyl-3-buten-1-ol (Entry 3 in Table 3). TLC
Rf 0.26 (1:5 ethyl acetate/hexane); IR (neat) 3625–3125, 3079,
3023, 2979, 2921, 1636, 1607, 1489, 1462, 1414, 1379, 1302,
1200, 1181, 1038, 999, 918 cmꢀ1; 1H NMR (300 MHz, CDCl3) δ
2.15 (s, 1 H, OH), 2.32 (s, 3 H, CH3), 3.10 (dd, 1 H, J ꢁ 7.0, 15.0
Hz, CH), 4.84 (d, 1 H, J ꢁ 6.9 Hz, CH), 5.01 (d, 1 H, J ꢁ 17.0 Hz,
vinyl), 5.02 (d, 1 H, J ꢁ 10.2 Hz, vinyl), 5.16 (d, 1 H, J ꢁ 17.3
Hz, vinyl), 5.25 (d, 1 H, J ꢁ 10.4 Hz, vinyl), 5.71 (ddd, 1 H, J ꢁ
6.9, 10.7, 17.9 Hz, vinyl), 5.90 (ddd, 1 H, J ꢁ 8.5, 8.5, 16.8 Hz,
vinyl), 7.10–7.24 (m, 3 H, aromatic), 7.41 (d, 1 H, J ꢁ 7.4 Hz, ar-
omatic); 13C NMR (75 MHz, CDCl3) δ 19.5, 55.3, 71.9, 116.7,
118.5, 126.0, 126.4, 127.3, 130.2, 135.0, 136.6, 136.8, 140.1; [α]D29
ꢃ69.7˚ (c 1.0, CHCl3). Found: C, 82.76; H, 8.81%. Calcd for
C13H16O: C, 82.94; H, 8.57%. The γ/ε ratio was determined to be
> 99/1 by 1H NMR analysis. The enantioselectivity of the γ-prod-
uct was determined to be 90% ee by HPLC analysis using a chiral
column (Chiralcel OD-H, Daicel Chemical Industries, Ltd., hex-
ane/i-PrOH ꢁ 20/1, flow rate ꢁ 0.5 mL/min): tminor ꢁ 14.7 min,
ε ratio was determined to be > 99/1 by H NMR analysis. The
enantioselectivity of the γ-product was determined to be 89% ee
by HPLC analysis using a chiral column (Chiralpak AD, Daicel
Chemical Industries, Ltd., hexane/i-PrOH ꢁ 100/1, flow rate ꢁ
0.5 mL/min): tminor ꢁ 31.8 min, tmajor ꢁ 33.3 min.
(E)-1-Phenyl-4-vinyl-1,5-hexadien-3-ol (Entry 6 in Table
3).13h–k TLC Rf 0.24 (1:5 ethyl acetate/hexane); IR (neat) 3640–
3130, 3081, 3027, 2980, 2872, 1636, 1541, 1509, 1495, 1449,
1
997, 967, 920 cmꢀ1; H NMR (300 MHz, CDCl3) δ 2.03 (s, 1 H,
OH), 2.99 (dd, 1 H, J ꢁ 7.7, 14.3 Hz, CH), 4.25 (t, 1 H, J ꢁ 6.0
Hz, CH), 5.12–5.25 (m, 4 H, vinyl), 5.79–5.93 (m, 2 H, vinyl),
6.22 (dd, 1 H, J ꢁ 6.3, 15.9 Hz, vinyl), 6.60 (dd, 1 H, J ꢁ 1.1,
15.9 Hz, vinyl), 7.20–7.39 (m, 5 H, aromatic); 13C NMR (75 MHz,
CDCl3) δ 55.0, 74.5, 117.7, 118.1, 126.6 (2 C), 127.8, 128.6 (2 C),
1
130.0, 131.6, 136.7; [α]D29 ꢃ11.9˚ (c 1.0, CHCl3). The IR and H
NMR spectra data indicated good agreement with reported data.13i
1
The γ/ε ratio was determined to be > 99/1 by H NMR analysis.
The enantioselectivity of the γ-product was determined to be 58%
ee by HPLC analysis using a chiral column (Chiralcel OD-H, Da-
icel Chemical Industries, Ltd., hexane/i-PrOH ꢁ 20/1, flow rate ꢁ
0.5 mL/min): tmajor ꢁ 23.8 min, tminor ꢁ 37.7 min.
1-Phenyl-4-vinyl-5-hexen-3-ol (Entry 8 in Table 3).13h–j
TLC Rf 0.26 (1:5 ethy acetate/hexane); IR (neat) 3700–3140,
3079, 3027, 2979, 2861, 1636, 1603, 1497, 1455, 1046, 999, 918
cmꢀ1; 1H NMR (300 MHz, CDCl3) δ 1.62–1.70 (m, 1 H, one pro-
ton of CH2), 1.75 (d, 1 H, J ꢁ 4.4 Hz, OH), 1.80–1.92 (m, 1 H,
one proton of CH2), 2.61–2.71 (m, 1 H, CH), 2.78–2.90 (m, 2 H,
CH2), 3.56 (m, 1 H, CH), 5.09–5.21 (m, 4 H, vinyl), 5.72–5.87 (m,
2 H, vinyl), 7.15–7.30 (m, 5 H, aromatic); 13C NMR (75 MHz,
CDCl3) δ 32.2, 36.1, 55.3, 72.5, 117.2, 117.9, 125.9, 128.5 (2 C),
128.6 (2 C), 137.0, 137.4, 142.3; [α]2D6 ꢀ9.4˚ (c 1.0, CHCl3). The
1
tmajor ꢁ 15.5 min.
IR and H NMR spectral data indicated good agreement with re-
1
1-(p-Methoxyphenyl)-2-vinyl-3-buten-1-ol (Entry 4 in Table
ported data.13i The γ/ε ratio was determined to be > 99/1 by H
3).13d TLC Rf 0.15 (1:5 ethyl acetate/hexane); IR (neat) 3710–
NMR analysis. The enantioselectivity of the γ-product was deter-
mined to be 71% ee by HPLC analysis using a chiral column
(Chiralcel OD-H, Daicel Chemical Industries, Ltd., hexane/i-
PrOH ꢁ 20/1, flow rate ꢁ 0.5 mL/min): tmajor ꢁ 16.9 min, tminor ꢁ
25.4 min.
3140, 3079, 3002, 2979, 2907, 2838, 1634, 1613, 1586, 1514,
1
1464, 1443, 1418, 1304, 1248, 1174, 1036, 1001, 918 cmꢀ1; H
NMR (300 MHz, CDCl3) δ 2.23 (d, 1 H, J ꢁ 2.7 Hz, OH), 3.07
(dt, 1 H, J ꢁ 7.4, 15.4 Hz, CH), 3.79 (s, 3 H, CH3), 4.51 (dd, 1 H,
J ꢁ 2.7, 7.4 Hz, CH), 4.99 (d, 1 H, J ꢁ 14.3 Hz, vinyl), 5.03 (d, 1
H, J ꢁ 7.7 Hz, vinyl), 5.18 (d, 1 H, J ꢁ 17.9 Hz, vinyl), 5.23 (d, 1
H, J ꢁ 10.4 Hz, vinyl), 5.65 (ddd, 1 H, J ꢁ 7.1, 10.7, 17.6 Hz, vi-
nyl), 5.84 (ddd, 1 H, J ꢁ 8.2, 10.4, 18.7 Hz, vinyl), 6.86 (d, 2 H, J
ꢁ 8.8 Hz, aromatic), 7.22 (d, 2 H, J ꢁ 8.5 Hz, aromatic); 13C
NMR (75 MHz, CDCl3) δ 55.3, 56.3. 75.9, 113.6 (2 C), 117.0,
118.3, 128.2 (2 C), 134.0, 136.9, 137.2, 159.1; [α]2D9ꢃ59.9˚ (c 1.0,
This work was supported in part by the Ministry of Educa-
tion, Science, Sports and Culture of the Japanese Government.
A. Yanagisawa acknowledges financial support from the Naito
Foundation and the Takeda Science Foundation.
1
CHCl3). The γ/ε ratio was determined to be > 99/1 by H NMR
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