Nickel(o)-catalysed asymmetric cross-coupling reactions of allylic compounds with Grignard reagents using optically active oxazolinylferrocenylphosphines as ligands

Article abstract of DOI:10.1039/b002547j

Optically active oxazolinylferrocenylphosphines work effectively as chiral P-N ligands in nickel(o)-catalysed cross-coupling reactions of allylic compounds with Grignard reagents, which are known to behave as hard nucleophiles, to give the expected coupling products in high yields and high enantioselectivities (30-100% chemical yield and 14-95% ee). These ligands are revealed to be more effective than optically active oxazolinylphenylphosphines which have only a central chirality. The Royal Society of Chemistry 2000.

Full text of DOI:10.1039/b002547j

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Nickel(0)-catalysed asymmetric cross-coupling reactions of allylic
compounds with Grignard reagents using optically active
oxazolinylferrocenylphosphines as ligands
1
Kang-Go Chung, Yoshihiro Miyake and Sakae Uemura*
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering,
Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan
Received (in Cambridge, UK) 30th March 2000, Accepted 15th June 2000
Published on the Web 19th July 2000
Optically active oxazolinylferrocenylphosphines work effectively as chiral P–N ligands in nickel(0)-catalysed
cross-coupling reactions of allylic compounds with Grignard reagents, which are known to behave as “hard”
nucleophiles, to give the expected coupling products in high yields and high enantioselectivities (30–100%
chemical yield and 14–95% ee). These ligands are revealed to be more effective than optically active
oxazolinylphenylphosphines which have only a central chirality.
attacks an allylic carbon directly [Scheme 1, path (B)].7 Excel-
lent selectivities have been attained using transition metal
catalysts with various chiral ligands in the allylation with “soft”
nucleophiles such as dimethyl malonate.8 However, examples of
the reaction with the corresponding “hard” nucleophiles are
quite limited, most of which are nickel-catalysed allylic sub-
stitutions with Grignard reagents in the presence of chiral P–P
ligands.9,10 Very recently, we reported that arylboronic acids
behave as “hard” nucleophiles in the cross-coupling reaction
with allylic compounds catalysed by nickel(0) with optically
active oxazolinylferrocenylphosphines as chiral P–N ligands
to give the corresponding arylated products with moderate
enantioselectivities (up to 53% ee).6 This, to the best of our
knowledge, was the first example of allylation using not
only organoheteroatom reagents but also chiral P–N ligands.
We have now disclosed that Grignard reagents can also be
employed as “hard” nucleophiles in place of arylboronic acids
in nickel(0)-catalysed asymmetric cross-coupling reaction of
allylic compounds using optically active oxazolinylferro-
cenylphosphines (Chart 1, I–V) as chiral P–N ligands, the
expected coupling products being obtained more stereo-
selectively. These phosphines have been revealed to be more
effective than the corresponding phosphines only having central
chirality such as VI.2d,3c
Introduction
Asymmetric synthesis catalysed by transition metals is now a
field of great attention and various kinds of optically active
ligands which coordinate to the metal have been devised in
order to achieve high enantioselectivities. Optically active
oxazolinylferrocenylphosphines (4,5-dihydrooxazolylferrocen-
ylphosphines) (Chart 1, I–V)1 having both planar and central
Chart 1
chiralities function as such ligands quite effectively in several
reductive reactions such as rhodium()-, iridium()-, or
ruthenium()-catalysed hydrosilylation of ketones or imines2
and ruthenium()-catalysed transfer hydrogenation of
ketones.3 Furthermore, they are utilized in some carbon–carbon
bond forming reactions4 including palladium(0)5- or nickel(0)6-
catalysed allylic substitution reaction using either “soft” or
“hard” nucleophiles, respectively, to construct new carbon–
carbon bonds.
Mechanistically, the allylic substitution reaction with a
“hard” nucleophile is considered to proceed differently from
that with a “soft” nucleophile; a “hard” nucleophile attacks a
transition metal first [Scheme 1, path (A)], while a “soft” one
Results and discussion
First, similar reaction conditions to those employed in the
case of arylboronic acids6 were applied to the cross-coupling
reactions between Grignard reagents and allylic compounds;
namely, in tetrahydrofuran (THF) at reflux with 3-acetoxycyclo-
hexene (1a, 1 equiv.) and phenylmagnesium bromide (3 equiv.
to 1a, 1.0 M THF solution) in the presence of nickel() acetyl-
acetonate [Ni(acac)2] (5 mol%), diisobutylaluminium hydride
(DIBAL-H) (16 mol%), and an optically active oxazolinyl-
ferrocenylphosphine (I, 10 mol%) as a chiral ligand. However,
the reaction did not proceed well and the amount of desired
coupling product, 3-phenylcyclohexene (3w), was low and not
enough to measure its optical yield on a polarimeter. Next, the
reaction was conducted at room temperature with the other
conditions kept constant (Scheme 2); 3w was then obtained in
33% chemical yield with 84% ee after 17 h together with a by-
product, biphenyl (Table 1, Entry 1). The result is better than
the case using phenylboronic acid from the standpoint that
Scheme 1
DOI: 10.1039/b002547j
J. Chem. Soc., Perkin Trans. 1, 2000, 2725–2729
This journal is © The Royal Society of Chemistry 2000
2725

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Table 2 Effect of chiral ligands on nickel-catalysed asymmetric
substitutiona
Entry
Ligand
Yield (%)b
Ee (%)c
Ph–Ph (%)d
Scheme 2
1
2
3
4
5
6
I
83
74
100
94
80
91
86
32
76
84
71
52
23
29
44
26
33
36
II
Table 1 Nickel-catalysed cross-coupling reactions between 3-substi-
tuted cyclohexenes and phenylmagnesium halidesa
III
IV
V
Entry
1X 2w
Yield (%)b
Ee (%)c
Ph–Ph (%)d
VI
a Reaction conditions: 1c (0.50 mmol), PhMgCl (1.5 mmol, 2.0 M
THF solution), Ni(acac)2 (0.025 mmol), ligand (0.050 mmol),
THF (total 3 mL), at rt for 17 h. b Determined by GLC based on 1c.
c Determined by optical rotation; (S)-configuration predominated in all
cases. d Determined by GLC; 0.75 mmol of biphenyl corresponds to
100%.
1e
2
1a
1a
1a
1a
1b
1c
1c
1d
1e
1f
Br
Br
Cl
I
Br
Br
Cl
Br
Br
Br
33
97
53
63
79
93
83
98
36
95
84
84
87
74
69
88
84
87
82
15
15
64
13
45
47
60
23
57
45
68
3
4f
5
6
7
8
9
biphenyl was not observed either by carrying out the reactions
for shorter periods (0.5–8 h) than 17 h, by using a smaller
amount of PhMgBr (1.2 equiv. to 1a), or by a quite slow add-
ition of PhMgBr (2 h vs. 5 min).
10
a Reaction conditions: 1 (0.50 mmol), 2w (1.5 mmol, THF solution),
Ni(acac)2 (0.025 mmol), ligand I (0.050 mmol), THF (total 3 mL), at rt
for 17 h. b Determined by GLC based on 1. c Determined by optical
rotation; (S)-configuration predominated in all cases. d Determined by
GLC; 0.75 mmol of biphenyl corresponds to 100%. e In the presence of
DIBAL-H (0.080 mmol). f THF (total 5 mL).
Next, oxazolinylferrocenylphosphines other than I (Chart
1) were examined under the conditions of Entry 7 in Table 1
and typical results are shown in Table 2. The same trend was
seen as observed in the reactions using phenylboronic acid;
each ligand including V ((S,S,S)-[2-(4,5-diphenyl-4,5-dihydro-
1,3-oxazol-2-yl)ferrocenyl]diphenylphosphine, abbreviated as
(S)-DIPOF) was found to be efficient except II and, espe-
cially, the ligand IV showed similar effectiveness to I (84% ee,
Entry 4). It is noteworthy that in the reaction using the
ligand VI,11 which has no planar chirality, the product showed
only moderate enantioselectivity (52% ee, Entry 6). This result
clearly shows the importance of the presence of planar chirality
in I.
Using the conditions described above, the reactions of other
Grignard reagents (Chart 2) with 5- or 6-membered cyclic com-
pounds were carried out (Table 3). In each reaction using
cyclohexenyl compounds, the expected coupling products
were obtained with high enantioselectivities; especially 1d and
2-naphthylmagnesium bromide (2z, X = Br) underwent
coupling to give 3-(2-naphthyl)cyclohexene (3z) of 95% ee
(Entry 8). In the cases using sterically hindered 1-naphthyl or
2-naphthylmagnesium bromide, an improvement in chemical
yields was achieved by adding a catalytic amount of DIBAL-H
as a reductant (Entries 7 and 9). 3-(4-Methoxyphenyl)cyclo-
hexene (3x) was also prepared from 4-methoxyphenyl-
magnesium chloride (2x, X = Cl), but the chemical yield was
much lower (Entry 5). From a five-membered cyclic compound,
3-phenoxycyclopentene, the expected product was obtained
quantitatively, but with a moderate enantioselectivity (47% ee,
Entry 10).
the reaction proceeded even at room temperature with higher
enantioselectivity, whereas the compound 3w was not detected
by GLC analysis in the reaction using phenylboronic acid which
proceeded only under reflux in THF and in the presence of
potassium hydroxide.6 Furthermore, a drastic improvement in
chemical yield was observed when the reaction was carried out
in the absence of DIBAL-H which was employed as a reductant
of Ni() to Ni(0) (Entry 2). In this case, apparently the reactant
PhMgBr itself acted as a reducing agent. Hoping to achieve
higher selectivities, the experiments at temperatures below room
temperature were also attempted. In the reaction at 0 ЊC or
Ϫ20 ЊC, a slight decrease in enantioselectivity (69% ee and 72%
ee, respectively) as well as yield (81% and 79%, respectively) of
3w was observed, while 3w was obtained at Ϫ78 ЊC in trace
quantities. When phenylmagnesium chloride was used in place
of the bromide, the yield of 3w as well as the by-product,
biphenyl, was reduced without loss of any enantioselectivity of
3w (Entry 3), while the reaction using the iodide resulted in a
lower optical yield (Entry 4). As to the effect of the nature of
the leaving group (Chart 2), cyclohex-2-enyl carbonate (1b),
When the reaction was applied to an acyclic compound, 4-
phenoxypent-2-ene, the coupling products showed only moder-
ate enantioselectivities (Scheme 3, Table 4); in each case, the
formation of a small amount of its cis isomer (trans/cis = 92–
1
95/5–8) was observed by H-NMR analysis. Unsymmetrical
acyclic substrates, 1-phenoxyhex-2-ene and 1-phenoxybut-2-
ene, were also applied to this reaction system (Schemes 4 and 5).
In each case, the regioselectivity for the phenylated product
with a chiral center as well as the enantioselectivity of the
product was low.12,13
We believe that the catalytic cycle of this reaction is as follows
(cf. Scheme 1, path (a) and ref. 8): (1) reduction of Ni() to
Ni(0) by ArMgX producing biaryl where a chiral P–N ligand
coordinates to Ni(0), (2) oxidative addition of Ni(0) to an allylic
compound to give an allylic nickel() species, (3) nucleophilic
attack of a Grignard reagent to the nickel() species (trans-
metallation) to give an allylic arylnickel() species and (4)
reductive elimination to produce a cross-coupling product
and to regenerate Ni(0). However, details of the structure of the
Chart 2
3-methoxycyclohexene (1c) and 3-phenoxycyclohexene (1d)
could be employed in place of 1a (Entries 5–8), although a
slight decrease in both chemical and optical yields was observed
in the case of 1b. The utilization of cyclohex-2-enol (1e)
resulted in lower chemical yield (Entry 9) and a great decrease
in enantioselectivity was observed in the reaction with 3-bromo-
cyclohexene (1f, Entry 10). In contrast to the reactions using
phenylboronic acid where biphenyl was scarcely produced,
the formation of variable amounts of biphenyl was observed in
the reaction using phenylmagnesium bromide. Additionally, the
enhancement of selectivity for the formation of 3w over
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J. Chem. Soc., Perkin Trans. 1, 2000, 2725–2729

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Table 3 Effect of 3-substituted cyclohexenes and Grignard reagents on nickel-catalysed asymmetric allylic substitutiona
Entry
1
2 (X = Br)
Yield of 3 (%)b
Ee (%)
[α]D25
1
2
3
4
5
1c
1d
1c
1d
1d
1d
1d
1d
1d
—
2w
2w
2x
2x
2xf
2y
2y
2z
93
98
73
69
28
7
39
50
72
100i
88c
87c
91e
91e
85e
64e
80e
95e
88e
47c
Ϫ140 (c 0.53, benzene)d
Ϫ139 (c 0.53, benzene)d
Ϫ135 (c 0.30, EtOH)
6
7g
8
ϩ22 (c 0.50, EtOH)
9g
10
2z
Ϫ169 (c 0.50, EtOH)
Ϫ99 (c 0.60, CHCl3)j
h
2w
a Reaction conditions; the allylic compound (0.50 mmol), ArMgX (1.5 mmol, 1.0 M THF solution), Ni(acac)2 (0.025 mmol), ligand I (0.050
mmol), THF (total 3 mL), at rt for 17 h. b Determined by GLC based on the allylic compound. c Determined by optical rotation; (S)-configuration
predominated in all cases. d See ref. 16. e Determined by HPLC analysis using suitable chiral columns. f X = Cl. g In the presence of DIBAL-H (0.080
mmol). h 3-Phenoxycyclopentene was used. i The yield of 3-phenylcyclopentene. j See ref. 17.
Scheme 3
Table 4 Nickel-catalysed cross-coupling reactions between 4-phenoxy-
Scheme 5
pent-2-ene and Grignard reagentsa
column using helium as carrier gas. GLC yields were deter-
Entry
2 (X = Br)
Yield (%) of 4b
Ee (%)c
mined using bibenzyl or pentamethylbenzene as an internal
standard. Optical rotations were measured on JASCO DIP-
1000 instrument. HPLC analyses were carried out on an L-7300
instrument with an L-7400 detector (HITACHI) using a Daicel
Chiralcel OB, OD or OJ column. Column chromatographies
were performed with Merck silica gel 60.
1
2w
2x
2y
2z
90d
40
30
40e
37
2
3f
4
14g
38
49
a Reaction conditions; the allylic compound (0.50 mmol), ArMgBr
(1.5 mmol, 1.0 M THF solution), Ni(acac)2 (0.025 mmol), ligand I
(0.050 mmol), THF (total 3 mL), at rt for 17 h. b Determined by GLC
based on the allylic compound; trans/cis = 92–95/5–8. c Determined
by HPLC analysis. d Isolated yield. e (S)-configuration predominated.
Materials
Tetrahydrofuran (THF) was distilled from sodium benzo-
phenone ketyl under argon. Other commercially available
compounds including Ni(acac)2 (not dried) and diisobutyl-
aluminium hydride (DIBAL-H) were used without further
purification. Chiral oxazolinylferrocenylphosphines (I–V)1a,1b
as well as the compound VI11 were prepared by the reported
methods. Cyclohex-2-enol (1e) was prepared by reduction of
cyclohex-2-en-1-one with NaBH4 and CeCl3ؒ7H2O in meth-
anol.14 3-Acetoxycyclohexene (1a) and 1-acetoxyhex-2-ene were
prepared by acetylation of the corresponding alcohol with
acetic anhydride. Cyclohex-2-enyl carbonate (1b) was prepared
from 1e and methyl chlorocarbonate. 3-Methoxycyclohexene
was prepared by methylation of 1e with iodomethane. 3-Bromo-
cyclohexene (1f) was prepared by treatment of cyclohexene with
NBS (N-bromosuccinimide). All phenyl ethers were prepared
according to the literature procedure.15
f In the presence of DIBAL-H. g Determined by H-NMR analysis of
1
methyl ester derived from 4-(1-naphthyl)pent-2-ene in the presence of
Eu(hfc)3 (see Experimental).
Scheme 4
intermediate species as well as the origin of the high enantio-
selectivity are not yet clear at present.
In summary, we have found that optically active oxazolinyl-
ferrocenylphosphines function as chiral P–N ligands in
nickel(0)-catalysed cross-coupling reactions of allylic com-
pounds with Grignard reagents. The reaction proceeded at
much lower temperature than the case of similar coupling reac-
tions using arylboronic acids, and the desired coupling product
was obtained in higher yield with much higher enantioselectivi-
ties (up to 100% chemical yield and 95% ee).
General procedure for Ni(0)-catalysed cross-coupling reaction of
3-acetoxycyclohexene (1a) with phenylmagnesium bromide
(Table 1, Entry 1)
To a mixture of Ni(acac)2 (6.5 mg, 0.025 mmol), (S,S)-[2-(4-
isopropyl-4,5-dihydro-1,3-oxazol-2-yl)ferrocenyl]diphenyl-
phosphine (I, 24.0 mg, 0.050 mmol), and bibenzyl (as an
internal standard; 19.9 mg) in THF (0.5 mL) was added
DIBAL-H (1.0 M solution in hexane; 0.080 mL, 0.080 mmol) at
0 ЊC under nitrogen. After stirring for 30 min, a solution of
3-acetoxycyclohexene (1a, 70.1 mg, 0.50 mmol) in THF (1.0
mL) was added. Fifteen minutes later, the 1.0 M THF solution
of phenylmagnesium bromide (1.5 mL, 1.5 mmol) was added
dropwise (for about 5 min) at 0 ЊC to the mixture which was
stirred at rt for 17 h. The resulting mixture was quenched with a
saturated aqueous solution of ammonium chloride, extracted
three times with diethyl ether and the organic layer was dried
over MgSO4. The amount of the product 3w was determined by
Experimental
General
1H- and 13C-NMR spectra were measured on JEOL EX-400,
JEOL JNM-AL300, and JEOL JNM-GSX270 spectrometers
for solutions in CDCl3 with Me4Si as an internal standard.
GLC analyses were carried out with a Shimadzu GC-14A
instrument equipped with a CPB 10-S25-050 (Shimadzu, fused
silica capillary column, 0.33 mm × 25 m, 5.0 mm film thickness)
J. Chem. Soc., Perkin Trans. 1, 2000, 2725–2729
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GLC analysis. For isolation of 3w the solvent was evaporated
and the residue was purified by column chromatography using
hexane as an eluent. Typical spectroscopic data of the obtained
coupling products are as follows.
(1H, m, trans isomer), 3.76 (1H, m, cis isomer), 3.78 (3H, s),
5.39–5.49 (1H, m), 5.55–5.62 (1H, m), 6.84 (2H, d, J = 8.7 Hz),
7.12 (2H, d, J = 8.7 Hz); 13C-NMR δ = 17.88, 21.57, 41.45,
55.25, 113.73, 123.33, 128.00, 136.58, 138.62, 157.79. The
diastereoisomeric ratio could not be determined because the
peak of the allylic proton of the cis isomer overlaps with that
3-Phenylcyclohexene (3w). Colorless liquid; 1H-NMR δ =
1.49–2.11 (6H, m), 3.42 (1H, m), 5.71 (1H, m), 5.89 (1H, m),
7.16–7.33 (5H, m); 13C-NMR δ = 21.19, 25.01, 32.60, 41.85,
125.94, 127.71, 128.24, 128.33, 130.18, 146.64. The ee value and
the configuration of the product were determined using a polar-
imeter based on the reported rotation of an optically pure
(R)-3w, [α]D29 = ϩ159.6 (c 0.53, benzene).16
1
of the methyl protons of the methoxy group in the H-NMR
spectrum. The ee value was determined by HPLC analysis with
a Daicel Chiralcel OJ column (eluent: hexane).
4-(1-Naphthyl)pent-2-ene (4y). Colorless liquid; 1H-NMR
δ = 1.47 (3H, d, J = 6.8 Hz, trans isomer), 1.48 (3H, d, J = 7.0
Hz, cis isomer), 1.69 (3H, dt, J = 6.4, 1.4 Hz, trans isomer), 1.74
(3H, dd, J = 6.6 Hz, cis isomer), 4.24 (1H, m, trans isomer), 4.53
(1H, m, cis isomer), 5.46–5.80 (2H, m), 7.36–7.53 (4H, m), 7.70
(1H, d, J = 7.7 Hz), 7.84 (1H, m), 8.13 (1H, d, J = 7.7 Hz);
13C-NMR δ = 17.98, 21.06, 37.02, 123.43, 123.61, 124.13,
125.25, 125.58, 125.63, 126.56, 128.84, 131.44, 133.96, 135.82,
142.34. The diastereoisomeric ratio of 4y (trans/cis = 92/8) was
determined by 1H-NMR analysis and the ee value was
1
3-(4-Methoxyphenyl)cyclohexene (3x). Colorless liquid; H-
NMR δ = 1.48–1.67 (3H, m), 1.69–1.77 (1H, m), 1.95–2.01 (1H,
m), 2.06–2.10 (2H, m), 3.32–3.38 (1H, m), 3.79 (3H, s), 5.69
(1H, dd, J = 10.0, 2.2 Hz), 5.83–5.89 (1H, m), 6.84 (2H, d,
J = 8.5 Hz), 7.13 (2H, d, J = 8.5 Hz); 13C-NMR δ = 21.13, 25.03,
32.73, 40.97, 55.27, 113.69, 128.13, 128.61, 130.53, 138.81,
157.89. The ee value was determined by HPLC analysis with a
Daicel Chiralcel OB column (eluent: hexane).
1
determined by H-NMR analysis in the presence of Eu(hfc)3
(europium
tris[3-(heptafluoropropylhydroxymethylene)-(ϩ)-
1
3-(1-Naphthyl)cyclohexene (3y). Colorless liquid; H-NMR
camphorate]) after conversion of 4y to 2-(1-naphthyl)propionic
acid by a similar method for 4w and then into its methyl ester,
methyl 2-(1-naphthyl)propionate.
δ = 1.64–1.78 (3H, m), 2.15–2.21 (3H, m), 4.19–4.26 (1H, m),
5.83 (1H, dd, J = 10.0, 2.6 Hz), 5.98–6.05 (1H, m), 7.37–7.54
(4H, m), 7.72 (1H, dd, J = 7.4, 2.1 Hz), 7.87 (1H, dd, J = 7.4, 2.2
Hz), 8.13 (1H, d, J = 7.7 Hz); 13C-NMR δ = 20.86, 25.25, 30.91,
37.00, 123.41, 125.06, 125.27, 125.42, 125.71, 126.60, 126.77,
128.92, 130.22, 131.40, 134.10, 141.92; IR (neat) 724, 761, 778,
796, 2834, 2858, 2930, 3018, 3045, 3059 cmϪ1 (Anal. Calcd. for
C16H16: C, 92.26; H, 7.74. Found: C, 92.50; H, 7.83%). The ee
value was determined by HPLC analysis with a Daicel Chiralcel
OB column (eluent: hexane).
4-(2-Naphthyl)pent-2-ene (4z). Colorless liquid; 1H-NMR
δ = 1.42 (3H, d, J = 6.9 Hz), 1.69 (3H, dt, J = 6.0, 1.2 Hz, trans
isomer), 1.73 (3H, d, J = 1.4 Hz, cis isomer), 3.53–3.63 (1H, m,
trans isomer), 3.89–4.01 (1H, m, cis isomer), 5.44–5.57 (1H, m),
5.65–5.74 (1H, ddq, J = 15.3, 6.6, 1.4 Hz), 7.36 (1H, dd, J = 8.5,
1.9 Hz), 7.40–7.47 (2H, m), 7.62 (1H, s), 7.75–7.81 (3H, m);
13C-NMR δ = 17.94, 21.37, 42.41, 124.01, 124.93, 125.15,
125.81, 126.31, 127.55, 127.60, 127.84, 132.14, 133.64, 136.10,
143.91. The diastereoisomeric ratio of 4z (trans/cis = 95/5) was
1
3-(2-Naphthyl)cyclohexene (3z). Colorless liquid; H-NMR
δ = 1.62–2.23 (6H, m), 3.56–3.60 (1H, m), 5.81 (1H, dd,
J = 10.0, 2.1 Hz), 5.92–6.00 (1H, m), 7.35–7.61 (3H, m), 7.64
(1H, s), 7.76–7.88 (3H, m); 13C-NMR δ = 21.12, 25.09, 32.41,
41.91, 125.14, 125.79, 125.81, 126.71, 127.55, 127.58, 127.84,
128.64, 130.06, 132.16, 133.55, 144.06; IR (neat) 723, 744, 757,
815, 853, 2835, 2856, 2927, 3018, 3052 cmϪ1 (Anal. Calcd. for
C16H16: C, 92.26; H, 7.74. Found: C, 92.45; H, 7.70%). The ee
value was determined by HPLC analysis with a Daicel Chiralcel
OJ (eluent: hexane).
1
determined by H-NMR analysis and the ee value was deter-
mined by HPLC analysis with a Daicel Chiralcel OD column
(eluent: hexane).
1
3-Phenylhex-1-ene (5). Colorless liquid; H-NMR δ = 0.89
(3H, t, J = 7.8 Hz), 1.16–1.42 (2H, m), 1.65–1.71 (2H, m), 3.25
(1H, dt, J = 7.6, 7.6 Hz), 5.01 (1H, d, J = 13.9 Hz), 5.03 (1H, d,
J = 8.9 Hz), 5.95 (1H, ddd, J = 13.9, 8.9, 7.6 Hz), 7.17–7.19 (3H,
m), 7.26–7.31 (2H, m); 13C-NMR δ = 13.98, 20.62, 37.63, 49.62,
113.80, 126.05, 127.60, 128.39, 142.53, 144.67. The ee value
was determined by HPLC analysis with a Daicel Chiralcel OJ
column (eluent: hexane).
1
3-Phenylcyclopentene. Colorless liquid; H-NMR δ = 1.69–
1.76 (1H, m), 2.35–2.54 (3H, m), 3.89 (1H, m), 5.78 (1H, m),
5.93 (1H, m), 7.18–7.20 (3H, m), 7.25–7.31 (2H, m); 13C-NMR
δ = 32.50, 33.78, 51.32, 125.96, 127.20, 128.36, 131.91, 134.28,
146.52. The ee value and the configuration of the product were
determined by a polarimeter based on the reported rotation of
an optically pure product of (S)-configuration, [α]D30 = Ϫ212
(c 0.596, chloroform).17
1
1-Phenylhex-2-ene (6). Colorless liquid; H-NMR δ = 0.90
(3H, t, J = 7.3 Hz), 1.35–1.44 (2H, m), 2.00 (2H, dt, J = 6.8, 7.3
Hz, trans isomer), 2.14 (2H, dt, J = 7.1, 7.3 Hz, cis isomer), 3.33
(2H, d, J = 6.3 Hz, trans isomer), 3.40 (2H, d, J = 6.4 Hz, cis
isomer), 5.47–5.61 (2H, m), 7.17–7.19 (3H, m), 7.25–7.30 (2H,
m); 13C-NMR δ = 13.67, 22.59, 34.59, 39.05, 125.83, 128.30,
128.46, 128.88, 131.88, 141.14.
1
4-Phenylpent-2-ene (4w). Colorless liquid; H-NMR δ = 1.33
(3H, d, J = 7.3 Hz), 1.67 (3H, d, J = 7.3 Hz), 3.41 (1H, m, trans
isomer), 3.79 (1H, m, cis isomer), 5.42–5.65 (2H, m), 7.16–7.31
(5H, m); 13C-NMR δ = 17.88, 21.46, 42.33, 123.63, 125.90,
127.13, 128.32, 136.24, 146.48. The diastereoisomeric ratio of
3-Phenylbut-1-ene (7). Colorless liquid; 1H-NMR δ = 1.37
(3H, d, J = 7.1 Hz), 3.40–3.52 (1H, m), 5.01 (1H, m), 5.07
(1H, m), 6.01 (1H, ddd, J = 17.0, 10.4, 6.5 Hz), 7.16–7.23 (3H,
m), 7.28–7.33 (2H, m); 13C-NMR δ = 20.72, 43.17, 113.08,
126.09, 127.23, 128.39, 143.25, 145.56. The ee value was
determined by HPLC analysis with a Daicel Chiralcel OJ
column (eluent: hexane–iPrOH = 99:1) after conversion of 7 to
2-phenylpropionic acid and then into its methyl ester, methyl
2-phenylpropionate.
1
4w (trans/cis = 95/5) was determined by H-NMR analysis and
the ee value was determined by HPLC analysis with a Daicel
Chiralcel OJ column (eluent: hexane). The configuration of the
product was determined by a polarimeter after conversion of
4w into 2-phenylpropionic acid by an oxidative cleavage using
KMnO4 and NaIO4, based on the reported rotation of an
optically pure product of (S)-configuration of 2-phenyl-
propionic acid, [α]D = ϩ76.2 (c 3, chloroform).18
1
1-Phenylbut-2-ene (8). Colorless liquid; H-NMR δ = 1.68–
1.74 (3H, m), 3.32 (2H, m), 5.49–5.59 (2H, m), 7.20–7.34
(5H, m).
4-(4-Methoxyphenyl)pent-2-ene (4x). Colorless liquid; 1H-
NMR δ = 1.30 (3H, d, J = 7.0 Hz), 1.66 (3H, d, J = 6.1 Hz), 3.36
2728
J. Chem. Soc., Perkin Trans. 1, 2000, 2725–2729

View Article Online
7 T. Hayashi, M. Konishi and M. Kumada, J. Chem. Soc., Chem.
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