A chiral spirocyclic borate ligand as a catalyst for the enantioselective Nozaki-Hiyama-Kishi allylation of arylaldehydes

Article abstract of DOI:10.1016/j.tetasy.2010.12.008

A chiral spirocyclic borate catalyst was used in the enantioselective Nozaki-Hiyama-Kishi allylation of arylaldehydes to determine the relationship between enantioselectivity and the Hammet constant for the production of homoallyl alcohols.

Full text of DOI:10.1016/j.tetasy.2010.12.008

Tetrahedron: Asymmetry 21 (2010) 2999–3004
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Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
A chiral spirocyclic borate ligand as a catalyst for the enantioselective
Nozaki–Hiyama–Kishi allylation of arylaldehydes
⇑
Xin-Ren Huang, Chinpiao Chen
Department of Chemistry, National Dong Hwa University, Shoufeng, Hualien 974, Taiwan, ROC
a r t i c l e i n f o
a b s t r a c t
Article history:
A chiral spirocyclic borate catalyst was used in the enantioselective Nozaki–Hiyama–Kishi allylation of
arylaldehydes to determine the relationship between enantioselectivity and the Hammet constant for
the production of homoallyl alcohols.
Received 5 November 2010
Accepted 9 December 2010
Available online 14 January 2011
Ó 2010 Elsevier Ltd. All rights reserved.
1
. Introduction
As an area of asymmetric synthesis, the enantioselective forma-
Ph
Ph
tion of C–Cbonds throughthe addition ofcarbonnucleophiles to car-
bonyl compounds has been extensively explored. The asymmetric
version of the Nozaki–Hiyama–Kishi (NHK) reaction is a notable
protocol for this kind of transformation that allows for the addition
of organochromium fragments to aldehydes and ketones with high
O
N
N+
B-
R
O
N
N
OH
OH
N
N
B-
N
N
HO O
Ph
HO O
Ph
Ph
Ph
1
Ph
Ph
enantioselectivity. Some interesting features of the NHK reaction
are its mild reaction conditions compatible to a variety of functional
2
2: R = Isopropyl
groups and the formation with versatile synthetic intermediates. In
5
3
4
: R = Benzyl
particular, the asymmetric addition of allylchromiums to aldehydes
: R = tert-Butyl
1
3
,4
and ketones is accomplished with higher enantioselectivity
when compared to that obtained with other allylation procedures
Figure 1. Chiral bipyridyl and chiral spirocyclic borate ligands used for aldehyde
allylation.
5
6
7
employing allyltin, allyborane, or allylsilanes. Recently, we dem-
onstrated the NHK allylation of ketones with good yields and high
enantioselectivities (up to 97%) with the new chiral spirocyclic bo-
8
30ꢀ35% overall yield. The diastereomer of 2, optimized for ketone
8
rate ligand 2. The high degree of asymmetric induction observed
allylation, was used as such for the present investigation and no
further stereochemical diversity of 2 was explored. A series of four
chiral ligands 2–5, varying at the alkyl group of the aminoalcohol
moiety, were used in the study. For comparison, bipyridyl ligand
with more difficult NHK reaction substrates (ketones) encouraged
us to examine the application of the ligand 2 for various aldehydes.
The electronic effects of substrates on enantioselectivity in var-
ious asymmetric transformations have been explored to provide
1
0a
1 was synthesized as reported.
With a full set of chiral ligands
9
insight into their mechanism. Earlier, our group explored similar
in hand, we set out to examine their application in the NHK allyla-
tion of benzaldehyde. The active catalyst was formed in situ by
reacting the chiral ligand with a catalytic amount of Cr(III) and a
base in a degassed and anhydrous solvent in the presence of an ex-
cess of Mn(0) as co-reductant and TMSCl. The addition of allyl re-
agents, followed by benzaldehyde, produced homoallylic alcohol 6
in good to moderate yield and enantioselectivity. The results ob-
tained for screening ligands 1–5 are given in Table 1.
The enantioselective outcome of the reaction was moderate in
the case of bipyridyl ligand 1 (Table 1, entry 1). On the other hand,
the enantioselectivity of reactions in the presence of spirocyclic bo-
rate ligands 2–5 was strongly dependant on the nature of the li-
gand’s aminoalcohol moiety and followed a similar trend, as
observed for ketone allylation. The best result was obtained with
2 (Table 1, entry 2), with the isopropyl group at the aminoalcohol
correlations for the asymmetric dialkylzinc addition to substituted
benzaldehydes, asymmetric Strecker reaction and asymmetric ring
opening of epoxides with thiols1 using chiral bipyridyl ligand 1.
Herein, the relationship between enantioselectivity and the Ham-
mett constants in the asymmetric NHK reaction of aromatic alde-
hydes in the presence of Cr(II)–2 complex is investigated (Fig. 1).
0
1
b
2
. Results and discussion
Chiral spirocyclic borate ligand 2 can be readily assembled from
various aminoalcohols and pinene derived bipyridyl ketone in a
⇑
Corresponding author. Tel.: +886 3 863 3597; fax: +886 3 863 0475.
E-mail address: chinpiao@mail.ndhu.edu.tw (C. Chen).
0
957-4166/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2010.12.008

3
000
X.-R. Huang, C. Chen / Tetrahedron: Asymmetry 21 (2010) 2999–3004
unit producing 6 in 81% ee and was, therefore, used for further
optimization studies.
enantioselection compared to the same substituents at the 3-posi-
tion. Conversely, electron withdrawing groups at the 2-position of
benzaldehyde afforded poor selectivity in comparison to the 3- and
4-positions. The correlations of ln([R]/[S]) with the Hammett con-
Allylation of benzaldehyde, in the presence of a Cr–2 catalyst,
was further optimized with respect to the nature of the solvents
and bases employed, catalyst loading, and allyl counterparts. The
optimization results are listed in Table 2. Of all solvents employed,
THF afforded the highest yield and enantioselectivity of 6 (Table 2,
entries 1ꢀ5). The reaction of benzaldehyde at lower temperatures
in the presence of TEA or replacing TEA with Hunig’s base or potas-
sium carbonate failed to produce any encouraging results (Table 2,
entries 6ꢀ8). The use of other allyl reagents was not as enantiose-
lective as allyl bromide. Allyl iodide produced similar activity with
a little loss in yield and asymmetric induction (Table 2, entry 10).
Low or no enantioselectivity was observed respectively for allyl
chloride and allylstannane (tetraallyl tin) (Table 2, entries 9 and
stants of both ortho-substituents (rortho) and para-substituents
(rpara) were performed using the Hammett equation ln([R]/
[S]) = rq. The corresponding Hammett plots for para- and ortho-
substituents are shown on Figure 3a and b, respectively. A concave
downward deviated Hammett plot with relatively large negative
r
values (ꢀ0.17 and ꢀ0.27) observed for para-substituted substrates
suggests that the coordination of the chromium complex with
aldehyde should be involved at least in the enantio-determination
step. The electron releasing groups increase the electron density of
the aryl moiety leading to enhanced
bipyridyl ring of the ligand and the benzaldehyde ring (Fig. 2).
p–p interaction between the
11
1
1). Reducing the catalyst loading to one-half with the optimized
The aromatic plane of bipyridine and benzaldehyde in an edge-
on arrangement (around 90°) generally leads to attraction. There-
fore, the benzaldehydes’ aromatic ring may be fixed tightly to the
bipyridine group of ligand 2 and the Re-face of carbonyl group
may favor allylation and thus increase enantioselectivity. This is
evident from the similar enantioselectivity observed for p-chloro-
benzaldehyde and benzaldehyde substituted with an electron-
donating substituent. A similar effect is observed in the case of
alkylation of substituted benzaldehydes using diethylzinc,1 and
the asymmetric trimethylsilylcyanation of substituted benzalde-
condition was equally effective but required a slightly longer reac-
tion time (Table 2, entry 12). The lower catalyst loading was fur-
ther used as an optimized catalyst loading for the substrate
screening. When CrBr
tivity was 77%ee.
Substituted benzaldehydes with electron releasing and electron
withdrawing substituents were reacted in the presence of Cr–2
complexes under the optimized conditions and the results are
shown in Table 3. All of the positional isomers were employed to
study the electronic effects of the substituent on the enantioselec-
tive outcome of the reaction. Substrates with electron-donating
groups at the 2- and 4-positions afforded a high degree of
3
was used in this reaction, the enantioselec-
0a
1
0b
hydes using trimethylsilylcyanide.
ortho-Substitution shows a
similar trend in the variation of enantiomeric excesses, with a lin-
ear Hammett plot.
Table 1
Nozaki–Hiyama–Kishi allylation of benzaldehyde catalyzed by a Cr(II) complex formed from chiral ligands 1–
5
O
OH
1
. CrCl3 (10 mol%), Mn (1.5 eq),
ligand (10 mol%), TEA (20mol%),
TMSCl (1.5 eq),THF, rt , 20 h
H
+
*
Br
(3.0 eq)
2. 1 M TBAF
6
Entry
Ligand
Yielda (%)
eeb (%)
1
2
3
4
5
1
2
3
4
5
75
83
80
81
77
69
81
25
39
25
a
Isolated yields after column chromatography.
Determined by chiral HPLC using Chiralcel OD-H column.
b
Table 2
Nozaki–Hiyama–Kishi allylation reactions of benzaldehyde catalyzed by Cr(II)–2 under various conditions
c
Entry
Solvent
CH CN
Ether
CH Cl
Toluene
THF
THF
THF
THF
THF
T (°C)
Base
Allyl halide
Ligand (mol %)
Yielda (%)
eeb (%)
1
2
3
4
5
6
7
8
9
3
rt
rt
rt
rt
rt
5
rt
rt
rt
rt
rt
rt
TEA
TEA
TEA
TEA
TEA
TEA
K CO
2 3
DIPEA
TEA
Allyl bromide
Allyl bromide
Allyl bromide
Allyl bromide
Allyl bromide
Allyl bromide
Allyl bromide
Allyl bromide
Allyl chloride
Allyl iodide
10
10
10
10
10
10
10
10
10
10
10
5
39
—
55
—
2
2
70
55
83
65
75
78
61
76
70
82
35
13
81
71
62
67
19
75
0
10
11
12
THF
THF
THF
TEA
TEA
TEA
Tetraallyl tin
Allyl bromide
81
a
b
c
Isolated yields after column chromatography.
Determination by chiral HPLC (Chiralcel OD-H column).
Reaction conditions: CrCl (5 mol %), Mn (1.5 equiv), solvent (2 mL), ligand 2 (5 mol %), base (10 mol %), allyl halide (3.0 equiv) and TMSCl (1.5 equiv) at room
3
temperature.

X.-R. Huang, C. Chen / Tetrahedron: Asymmetry 21 (2010) 2999–3004
3001
Table 3
Nozaki–Hiyama–Kishi allylation reactions of substituted benzaldehydes catalyzed by Cr(II)–2
O
OH
*
1
. CrCl (5 mol%), Mn (1.5 eq), Ligand 2 (5 mol%),
3
TEA (10 mol%), TMSCl (1.5 eq), THF, 20 h
H
+ Br
R
2
. 1 M TBAF
R
(
3.0 eq)
6
-18
Yielda (%)
eeb (%)
Hammett constants12
T
D
Configuration
Entry
R
Products
½
aꢁ
(T °C, c) CH Cl2
2
1
2
3
4
5
6
7
8
9
0
1
2
3
H
6
7
8
83
77
72
68
80
70
73
70
78
75
54
45
60
81
74
46
80
61
56
77
r
r
r
r
r
r
r
r
r
r
r
r
r
, 0
+44.5 (25, 1.13)
+57.5 (26, 1.25)
+35.7 (26.4, 1.50)
+44.6 (26.8, 1.63)
+41.9 (25, 2.49)
+29.4 (25.4, 1.10)
+39.1 (26, 1.73)
+61.6 (25, 0.70)
+39.2 (24.5, 1.10)
+43.6 (23.7, 1.00)
+9.2 (25, 0.85)
(R)
(R)
(R)
(R)
(R)
(R)
(R)
(R)
(R)
(R)
na
o-OMe
o
,+0.12
d
c
c
m-OMe
p-OMe
o-Me
m-Me
p-Me
o-Cl
m-Cl
p-Cl
o-CN
m-CN
p-CN
m
, +0.12
9
p
, ꢀ0.27
, +0.29
, ꢀ0.07
, ꢀ0.17
, +1.28
, +0.37
, +0.23
, +1.06
, +0.56
, +0.66
10
11
12
13
14
15
16
17
18
o
m
p
c
9
o
78
79
9
45
47
m
c
c
1
1
1
1
p
o
m
+15.3 (25.2, 0.40)
+20.9 (26, 1.20)
na
na
p
a
b
c
Isolated yields after column chromatography.
Determination by chiral HPLC (Chiralcel OD-H column).
The enantiometric excesses were determined from their benzoates.
d
The enantiometric excesses were determined by 1-(3-methoxy-phenyl)-butan-1-ol.
4
4
. Experimental
.1. General
All reactions were carried out in anhydrous solvents. THF
and diethyl ether were distilled from sodium-benzophenone under
argon. Toluene, CH CN, CH Cl , and hexane were distilled from
. H NMR spectra were obtained at 300 or 400 MHz (as indi-
3
2
2
1
CaH
2
1
3
cated), and C NMR spectra were obtained at 75.5 or 100.6 MHz
NMR spectrometer. Chemical shifts (d) are reported in ppm relative
to CDCl (7.26 and 77.0 ppm). Mass spectra (MS) and high resolu-
3
tion mass spectra (HRMS) were determined on a mass spectrome-
ter. Infrared spectra were recorded using a FT/IR spectrometer. All
asymmetric reactions were conducted in dry glassware under
nitrogen using a standard glovebox. Enantiomeric excesses were
determined using high performance liquid chromatography (HPLC)
with a Chiracel OD-H chiral column. Optical rotations were mea-
sured using a polarimeter at the indicated temperature using a so-
Figure 2. The aromatic plane of bipyridine and benzaldehyde in an edge-on
arrangement (around 90°) generally leads to attraction.
3
. Conclusion
A class of bipyridine-containing ligands 2–5 were prepared.
The ligands were adopted in the chromium-catalyzed enantiose-
lective allylation of benzaldehyde with excellent conversion and
good enantioselectivity values of up to 81% ee. Again, the re-
sults reveal the significant effect of the moieties in the amino
acid derivative on the sense of asymmetric induction. The
Hammett substituent constants were correlated with the
enantiomeric excesses of homoallyl alcohols from the NHK ally-
lation of ortho- and para-substituted benzaldehydes using allyl
bromide.
dium lamp (D line, 589 nm). Flash column chromatography was
performed using silica gel 60 (70–230 mesh).
4.2. Representative procedure for the Nozaki–Hiyama–Kishi
reaction
3
A mixture of CrCl (4.0 mg, 5 mol %) and Mn (83.0 mg,
0.75 mmol) in THF (2.00 mL) was stirred at room temperature for
a 2.5
b 2.5
p -OMe
H
o -OMe
2
H
2
1.5
1
p -Me
p -Cl
1
0
.5
1
Me
.5
0
o -Cl
p -CN
0.5
o -CN
-
0.5
0
-
-
0.1
0.1
0.3
0.5
0.7
o
0.9
1.1
1.3
0.3
-0.1
0.1
0.3
0.5
0.7
σ
σ
p
Figure 3. (a) The correlation of the Hammett constants (
o p
r ) and the enantiomeric excesses (ln(R/S)) and (b) the Hammett constants (r ) and the enantiomeric excesses of the
NHK allylation reaction of substituted benzaldehydes in the presence of a Cr(III)–2 complex.

3
002
X.-R. Huang, C. Chen / Tetrahedron: Asymmetry 21 (2010) 2999–3004
1
1
h, at which point ligand 2 (13.5 mg, 5 mol %) and TEA (7
0 mol %) were added. After 1 h stirring at room temperature, allyl
L, 1.5 mmol) was added and the solution was stirred
for another 1 h; benzaldehyde (50 L, 0.5 mmol) and TMSCl (93 L,
.75 mmol) were added and stirred at room temperature for 20 h.
l
L,
measured by HPLC (Chiralcel OD-H, 2-propanol/hexanes, 1:9,
0.25 mL/min) to be 46% ee.
bromide (65
l
l
l
4.2.4. 1-(4-Methoxy-phenyl)-but-3-en-1-ol 9
2
6:8
1
0
Yield: 68%. ½
CDCl ): d 7.29–7.25 (m, 2H), 6.91–6.87 (m, 2H), 5.87–5.73 (m,
1H), 5.18–5.11 (m, 2H), 4.70–4.67 (t, J = 4.5 Hz, 1H), 3.80 (s, 3H),
a
ꢁ
2 2
¼ þ44:6 (c 1.63, CH Cl ). H NMR (300 MHz,
D
The reaction was quenched by adding a saturated sodium bicar-
bonate solution (5 mL), and the solid residue was removed by fil-
tration through a plug of Celite. The filtrate was extracted with
dichloromethane (10 mL ꢂ 3), and the combined extracts were
dried over sodium sulfate. After the organic phase was filtered
and concentrated, the residue was dissolved in THF (2 mL), TBAF
3
1
3
2.52–2.47 (t, J = 7.5 Hz, 2H), 2.04 (s, 1H). C NMR (75.5 MHz,
CDCl ): d 159.0, 136.0, 134.6, 127.0, 118.2, 113.8, 73.0, 55.9, 43.7.
IR (KBr): 3417, 3082, 2934, 2830, 1641, 1612, 1587, 1513, 1470,
3
ꢀ1
1434, 1299, 1247, 1175, 1035, 916, 872, 832 cm . MS (EI) m/z:
+
(
1.5 mL, 1.5 mmol) was added slowly, and the solution was stirred
[M] 178 (0.4), 137 (100), 109 (38), 94 (29), 77 (31). HRMS-EI (m/
+
for 30 min. The reaction was quenched by adding a saturated
sodium bicarbonate solution (3 mL), and the aqueous phase was
extracted with dichloromethane (5 mL ꢂ 3). The combined ex-
tracts were dried over sodium sulfate. Following the filtration
and concentration of the organic phase, the residue was purified
by flash column chromatography using silica gel as the stationary
phase and ethyl acetate–hexane as the mobile phase to obtain 1-
phenyl-but-3-en-1-ol
CH
5
z): [M] calcd for C11
H
14
2
O , 178.0990; found, 178.0995. The enanti-
oselectivity was measured by HPLC (Chiralcel OD-H, 2-propanol/
hexanes, 1:9, 0.25 mL/min) to be 80% ee.
4.2.5. 1-o-Tolyl-but-3-en-1-ol 10
2
5:0
1
Yield: 80%. ½
CDCl ): d 7.50–7.47 (m, 1H), 7.47–7.15 (m, 3H), 5.87–5.73 (m,
1H), 5.22–5.14 (m, 2H), 5.00–4.96 (m, 1H), 2.52–2.42 (m, 2H),
aꢁ
¼ þ41:9 (c 2.49, CH
2 2
Cl ). H NMR (300 MHz,
D
3
2
D
5
6
(61 mg, 83%).
). H NMR (300 MHz, CDCl ): d 7.36–7.26 (m, 5H), 5.86–
.77 (m, 1H), 5.19–5.13 (m, 2H), 4.75–4.70 (m, 1H), 2.56–2.49
½
a
ꢁ
¼ þ44:5 (c 1.13,
1
13
2
Cl
2
3
3
2.34 (s, 3H), 1.86 (s, 1H). C NMR (100.6 MHz, CDCl ): d 141.9,
134.7, 134.3, 130.3, 127.2, 126.2, 125.1, 118.2, 69.7, 42.6, 19.0. IR
(KBr): 3379, 3073, 3023, 2976, 2932, 1640, 1605, 1486, 1460,
1434, 1380, 1287, 1215, 1179, 1049, 999, 915, 870, 756,
1
3
(
m, 2H), 2.17 (s, 1H). C NMR (75.5 MHz, CDCl
3
): d 143.9, 134.5,
1
2
(
28.4, 127.5, 125.8, 118.4, 73.3, 43.8. IR (KBr): 3389, 3082, 3028,
ꢀ1
ꢀ1
+
983, 2929, 2902, 1641, 1596, 1492, 1454, 757, 700 cm . MS
726 cm . MS (EI) m/z: [M] 162 (1.4), 121 (100), 93 (25), 91
EI) m/z: [M]+ 148 (0.2), 107 (100), 79 (88), 77 (48), 51 (12).
(14), 77 (7). HRMS-EI (m/z): [M] calcd for C11
+
H14O, 162.1045;
HRMS-EI (m/z): [M]+ calcd for
48.0882. The enantioselectivity was measured by HPLC (Chiralcel
OD-H, 2-propanol/hexanes, 1:9, 0.25 mL/min) to be 81% ee.
12O, 148.0888; found,
found, 162.1052.
10
C H
1
4
.2.6. Benzoic acid 1-o-tolyl-but-3-enyl ester 10a
1
3
H NMR (400 MHz, CDCl ): d 8.11–8.09 (m, 2H), 7.58–7.54 (m,
4
.2.1. 1-(2-Methoxy-phenyl)-but-3-en-1-ol 7
1
H), 7.48–7.43 (m, 3H), 7.22–7.18 (m, 3H), 6.29–6.26 (m, 1H),
2
6:0
1
Yield: 77.0%. ½
CDCl ): d 7.35–7.22 (m, 2H), 6.98–6.86 (m, 2H), 5.87–5.81 (m, 1H),
.17–5.09 (m, 2H), 4.98–4.94 (m, 1H), 3.85 (s, 3H), 2.64–2.48 (m,
aꢁ
2 2
¼ þ57:5 (c 1.25, CH Cl ). H NMR (300 MHz,
D
5.83–5.79 (m, 1H), 5.18–5.08 (m, 2H), 2.80–2.69 (m, 2H), 2.49 (s,
13
3
3
1
1
1
3
H). C NMR (100.6 MHz, CDCl ): d 165.7, 138.7, 135.0, 133.4,
5
3
1
3
1
32.9, 130.4, 129.6, 128.3, 127.7, 126.2, 125.8, 118.1, 72.6, 40.3,
9.3. IR (KBr): 3082, 3019, 2974, 2929, 2857, 1715, 1641, 1600,
492, 1451, 1313, 1273, 1070, 1021, 970, 921, 764, 710 cm . MS
1
3
3
H). C NMR (75.5 MHz, CDCl ,): d 156.3, 135.2, 131.8, 128.3,
26.8, 120.7, 117.5, 110.4, 69.6, 55.2, 41.9. IR (KBr): 3417, 3073,
002, 2937, 2836, 1639, 1601, 1588, 1490, 1463, 1287, 1240,
ꢀ1
+
(
EI) m/z: [M] 266 (0.1), 225 (19), 129 (12), 105 (100), 77 (30).
ꢀ1
+
048, 781, 754 cm . MS (EI) m/z: [M] 178 (0.6), 160 (10), 137
+
HRMS-EI (m/z): [M] calcd for
66.1311. The enantioselectivity was measured by HPLC (Chiralcel
OD-H, 2-propanol/hexanes, 1:9, 0.25 mL/min) to be 61% ee.
18 18 2
C H O , 266.1307; found,
+
(
100), 109 (40), 94 (31), 77 (27). HRMS-EI (m/z): [M] calcd for
, 178.0994; found, 178.0995. The enantioselectivity was
measured by HPLC (Chiralcel OD-H, 2-propanol/hexanes, 1:9,
2
11 14 2
C H O
0
.25 mL/min) to be 74% ee.
4
.2.7. 1-m-Tolyl-but-3-en-1-ol 11
2
5:4
1
Yield: 70%. ½
aꢁ
¼ þ29:4 (c 1.10, CH
2 2
Cl ). H NMR (400 MHz,
4
.2.2. 1-(3-Methoxy-phenyl)-but-3-en-1-ol 8
D
2
D
6:4
1
CDCl ): d 7.24–7.22 (d, J = 8.0 Hz, 1H), 7.18–7.14 (t, J = 8.0 Hz,
2
3
Yield: 72.0%. ½
aꢁ
¼ þ35:7 (c 1.50, CH
2 2
Cl ). H NMR (300 MHz,
H), 7.10–7.08 (d, J = 8.0 Hz, 1H), 5.87–5.76 (m, 1H), 5.19–5.13
CDCl ): d 7.29–7.26 (t, J = 4.5 Hz, 1H), 6.93–6.92 (t, J = 1.5 Hz, 2H),
6
1
3
(
m, 2H), 4.72–4.69 (m, 1H), 2.55–2.47 (m, 2H), 2.36 (s, 3H), 1.56
.83–6.80 (m, 1H), 5.85–5.76 (m, 1H), 5.19–5.12 (m, 2H), 4.71 (s,
H), 3.81 (s, 3H), 2.56–2.45 (m, 2H), 2.07 (s, 1H). 13C NMR
1
3
(s, 1H).
3
C NMR (100.6 MHz, CDCl ): d 143.8, 138.0, 134.5,
1
3
1
28.32, 128.30, 126.4, 122.8, 118.3, 73.3, 43.8, 21.4. IR (KBr):
388, 3074, 3023, 2977, 2920, 2866, 1641, 1608, 1590, 1487,
432, 1156, 1049, 997, 915, 786, 703 cm . MS (EI) m/z: [M] 162
(
3
75.5 MHz, CDCl ): d 159.7, 145.6, 134.4, 129.4, 118.4, 118.1,
1
2
7
13.0, 111.3, 73.2, 68.3, 55.2, 43.8. IR (KBr): 3417, 3073, 3010,
937, 2836, 1641, 1601, 1587, 1487, 1461, 1263, 1155, 1043,
ꢀ1
+
+
ꢀ1
+
(0.3), 121 (100), 93 (80), 91 (48), 77 (34). HRMS-EI (m/z): [M] calcd
for C11 14O, 162.1045; found, 162.1050. The enantioselectivity
was measured by HPLC (Chiralcel OD-H, 2-propanol/hexanes, 1:9,
.25 mL/min) to be 56% ee.
85, 754, 700 cm . MS (EI) m/z: [M] 178 (3.5), 137 (91), 109
+
H
(
100), 94 (42), 77 (42), 66 (19). HRMS-EI (m/z): [M] calcd for
C
4
6
11
H
14
O
2
, 178.0994; found, 178.0990.
0
.2.3. 1-(3-Methoxy-phenyl)-butan-1-ol 8a
1
H NMR (400 MHz, CDCl
3
): d 7.29–7.27 (t, J = 4.0 Hz, 1H), 7.25–
4.2.8. 1-p-Tolyl-but-3-en-1-ol 12
2
D
6:0
1
.93 (m, 2H), 6.83–6.81 (m, 1H), 4.69–4.65 (t, J = 8.0 Hz, 1H), 1.81
Yield: 73%. ½
CDCl ): d 7.26–7.24 (d, J = 8.0 Hz, 2H), 7.17–7.15 (d, J = 8.0 Hz,
2H), 5.86–5.76 (m, 1H), 5.19–5.12 (m, 2H), 4.71–4.68 (m, 1H),
2.52–2.49 (m, 2H), 2.35 (s, 3H), 2.07 (s, 1H).
(100.6 MHz, CDCl ): d 140.9, 137.1, 134.6, 129.1, 125.8, 118.19,
73.2, 43.7, 21.1. IR (KBr): 3390, 3075, 3009, 2977, 2922, 1902,
1640, 1615, 1513, 1432, 1309, 1198, 1179, 1106, 1044, 998, 914,
871, 816, 537 cm . MS (EI) m/z: [M] 162 (0.3), 121 (100), 93
aꢁ
¼ þ39:1 (c 1.73, CH
2 2
Cl ). H NMR (400 MHz,
(
s, 1H), 1.81–1.66 (m, 2H), 1.47–1.32 (m, 2H), 0.97–0.93 (t,
3
1
3
J = 4.0 Hz, 3H).
3
C NMR (100.6 MHz, CDCl ): d 159.7, 146.7,
13
1
3
1
29.4, 118.2, 112.9, 111.4, 74.3, 55.2, 41.2, 19.0, 13.9. IR (KBr):
360, 3064, 2959, 2929, 2866, 1600, 1573, 1470, 1432, 1384,
198, 1028, 785, 746, 698 cm . MS (EI) m/z: [M] 180 (32), 137
C NMR
3
ꢀ1
+
+
(
C
100), 109 (58), 94 (34), 77 (35). HRMS-EI (m/z): [M] calcd for
, 180.1150; found, 180.1152. The enantioselectivity was
ꢀ
1
+
11
H
16
O
2

X.-R. Huang, C. Chen / Tetrahedron: Asymmetry 21 (2010) 2999–3004
3003
(
35), 91 (30), 77 (25). HRMS-EI (m/z): [M]+ calcd for C11
62.1045; found, 162.1046.
H
14O, 4.2.14. Benzoic acid 1-(4-chloro-phenyl)-but-3-enyl ester 15a
1
1
4
1
H NMR (300 MHz, CDCl
.54 (t, J = 7.5 Hz, 1H), 7.47–7.42 (t, J = 7.5 Hz, 2H), 7.38–7.31 (m,
4H), 6.04–5.99 (t, J = 7.5 Hz, 1H), 5.82–5.73, (m, 1H), 5.15–5.07
3
): d 8.09–8.06 (d, J = 6.0 Hz, 2H), 7.59–
7
.2.9. Benzoic acid 1-p-tolyl-but-3-enyl ester 12a
1
13
3
H NMR (400 MHz, CDCl ): d 8.10–8.08 (m, 2H), 7.58–7.54 (m,
3
(m, 1H), 2.82–2.65 (m, 2H). C NMR (75.5 MHz, CDCl ): d 165.6,
H), 7.46–7.42 (m, 2H), 7.35–7.33 (d, J = 8.0 Hz, 2H), 7.19–7.17
d, J = 8.0 Hz, 2H), 6.06–6.04 (t, J = 4.0 Hz, 1H), 5.84–5.77 (m,
138.7, 133.7, 133.1, 132.8, 130.2, 129.6, 128.7, 128.4, 127.9,
118.6, 75.1, 40.8. IR (KBr): 3066, 2924, 2844, 1720, 1640, 1604,
1582, 1488, 1449, 1413, 1342, 1320, 1268, 1177, 1102, 1071,
(
1
1
3
H), 5.17–5.06 (m, 2H), 2.84–2.70 (m, 2H), 2.37 (s, 1H).
): d 165.7, 137.7, 137.2, 133.4, 132.8,
30.5, 129.6, 129.1, 128.3, 126.5, 118.0, 75.7, 40.8, 21.1. IR
KBr): 3064, 3028, 2938, 2866, 1715, 1645, 1605, 1583, 1515,
C
ꢀ1
+
NMR (100.6 MHz, CDCl
1
(
3
1026, 982, 919, 822, 711, 529 cm . MS (EI) m/z: [M] 286 (0.05),
245 (7), 139 (10), 129 (15), 105 (100), 77 (62), 51 (19). HRMS-EI
+
(m/z): [M] calcd for C17
H
15ClO
2
, 286.0761; found, 286.0752. The
1
8
443, 1345, 1313, 1270, 1178, 1109, 1070, 1029, 975, 921,
enantioselectivity was measured by HPLC (Chiralcel OD-H, 2-pro-
panol/hexanes, 1:9, 0.25 mL/min) to be 79% ee.
ꢀ
1
+
14, 710, 683 cm . MS (EI) m/z: [M] 266 (0.1), 225 (22), 105
+
(
100), 77 (21). HRMS (EI): [M] calcd for C18
found, 266.1313. The enantioselectivity was measured by HPLC
Chiralcel OD-H, 2-propanol/hexanes, 1:9, 0.25 mL/min) to be
18 2
H O , 266.1307;
4
.2.15. 2-(1-Hydroxy-but-3-enyl)-benzonitrile 16
(
25:0
). 1H NMR (400 MHz,
2 2
Cl
Yield: 54%. ½
a
ꢁ
¼ þ9:2 (c 0.85, CH
D
7
7% ee.
CDCl ): 7.85–7.83 (d, J = 8.0 Hz, 1H), 7.56–7.52 (m, 1H),
3
d
7
1
.52–7.44 (m, 1H), 7.36–7.34 (d, J = 8.0 Hz, 1H), 5.83–5.73 (m,
4
.2.10. 1-(2-Chloro-phenyl)-but-3-en-1-ol 13
H), 5.51–5.48 (t, J = 6.0 Hz, 1H), 5.19–5.12 (m, 2H), 2.73–2.55
2
5:0
1
Yield: 70%. ½
CDCl ): d 7.58–7.55 (t, J = 4.5 Hz, 1H), 7.34–7.18 (m, 3H), 5.88–
.83 (m, 1H), 5.22–5.14 (m, 3H), 2.66–2.59 (m, 1H), 2.43–2.36
m, 1H), 2.06 (s, 1H). 13C NMR (75.5 MHz, CDCl
): d 141.1, 134.2,
aꢁ
¼ þ61:6 (c 0.70, CH
2
Cl
2
). H NMR (300 MHz,
13
D
3
(m, 2H). C NMR (100.6 MHz, CDCl ): d 167.9, 146.7, 131.9,
3
1
2
1
7
29.4, 128.8, 123.8, 121.6, 119.0, 82.1, 39.3; IR (KBr): 3293, 3077,
978, 2910, 2222, 1940, 1840, 1763, 1681, 1614, 1468, 1431,
368, 1305, 1264, 1238, 1206, 1153, 1101, 1047, 921, 836, 780,
5
(
3
1
2
1
31.7, 129.4, 128.4, 127.1, 118.7, 69.6, 42.0. IR (KBr): 3389, 3073,
983, 2920, 2857, 1637, 1600, 1573, 1470, 1434, 1200, 1129,
ꢀ1
+
41, 711, 663, 565 cm ; MS (EI) m/z: [M+1] 174 (3.2), 133
+
(
100), 105 (40), 77 (40), 51 (17). HRMS-EI (m/z): [M] calcd for
11NO, 173.0841; found, 173.0834. The enantioselectivity was
measured by HPLC (Chiralcel OD-H, 2-propanol/hexanes, 1:9,
.25 mL/min) to be 9% ee.
ꢀ1
+
033, 994, 921, 754, 701 cm . MS (EI) m/z: [M] 182 (0.8), 143
11
C H
(
24), 141 (100), 113 (37), 78 (9). HRMS-EI (m/z): [M]+ calcd for
C
10
H11ClO, 182.0498; found, 182.0502.
0
4
.2.11. Benzoic acid 1-(2-chloro-phenyl)-but-3-enyl ester 13a
1
4.2.16. 3-(1-Hydroxy-but-3-enyl)-benzonitrile 17
3
H NMR (400 MHz, CDCl ): d 8.12–8.10 (t, J = 4.0 Hz, 2H), 7.60–
2
5:2
1
Yield: 45%. ½
CDCl ): d 7.67 (s, 1H), 7.60–7.54 (m, 2H), 7.46–7.43 (t, J = 6.0 Hz,
1H), 5.82–5.72 (m, 1H), 5.19–5.14 (m, 2H), 4.79–4.76 (m, 1H),
a
ꢁ
2 2
¼ þ15:3 (c 0.40, CH Cl ). H NMR (400 MHz,
D
7
1
5
.56 (t, J = 4.0 Hz, 1H), 7.50–7.44 (m, 3H), 7.39–7.37 (t, J = 4.0 Hz,
H), 7.26–7.21 (m, 2H), 6.47–6.43 (m, 1H), 5.87–5.82 (m, 1H),
.16–5.08 (m, 2H), 2.78–2.73 (m, 2H);
3
13
C NMR (100.6 MHz,
1
3
2
1
7
3
.56–2.43 (m, 2H), 2.42 (s, 1H). C NMR (100.6 MHz, CDCl ): d
CDCl3): d 165.4, 138.1, 133.0, 132.9, 132.1, 130.2, 129.6, 128.8,
45.31, 133.3, 131.1, 130.2, 129.5, 129.1, 119.4, 118.8, 112.4,
2.1, 43.8. IR (KBr): 3443, 3073, 3010, 2983, 2924, 2230, 1642,
1
1
1
28.4, 127.1, 126.9, 118.3, 72.5, 39.5. IR (KBr): 3073, 2929, 2857,
724, 1641, 1605, 1451, 1358, 1335, 1318, 1267, 1178, 1107,
ꢀ1
+
1605, 1587, 1479, 1433, 1308, 1227, 1156, 1056, 994, 919, 867,
070, 1024, 984, 926, 755, 710 cm . MS (EI) m/z: [M] 286
ꢀ
1
+
8
01, 741, 694, 489 cm . MS (EI) m/z: [M] 173 (0.8), 132 (100),
(
(
0.03), 139 (18), 128 (18), 105 (100), 77 (73), 51 (22). HRMS-EI
+
m/z): [M]+ calcd for C17H15ClO2, 286.0761; found, 286.0755.
104 (6). HRMS-EI (m/z): [M] calcd for C
73.0833. The enantioselectivity was measured by HPLC (Chiralcel
OD-H, 2-propanol/hexanes, 1:9, 0.25 mL/min) to be 45% ee.
11
H11NO, 173.0841; found,
1
The enantioselectivity was measured by HPLC (Chiralcel OD-H, 2-
propanol/hexanes, 1:9, 0.25 mL/min) to be 9% ee.
4
.2.17. 4-(1-Hydroxy-but-3-enyl)-benzonitrile 18
4
.2.12. 1-(3-Chloro-phenyl)-but-3-en-1-ol 14
2
6:0
1
2
4:5
1
Yield: 60%. ½
CDCl ): d 7.65–7.62 (t, J = 6.0 Hz, 2H), 7.48–7.46 (d, J = 4.0 Hz,
H), 5.82–5.72 (m, 1H), 5.20–5.15 (m, 2H), 4.81–4.79 (t,
a
ꢁ
2 2
¼ þ20:9 (c 1.20, CH Cl ). H NMR (400 MHz,
Yield: 78%. ½
CDCl ): d 7.64 (s, 1H), 7.37–7.21 (m, 3H), 5.83–5.72 (m, 1H),
.20–5.15 (m, 2H), 4.74–4.69 (m, 1H), 2.55–2.42 (m, 2H), 2.04 (s,
a
ꢁ
¼ þ39:2 (c 1.10, CH
2
Cl
2
). H NMR (300 MHz,
D
D
3
3
2
5
1
1
2
1
13
H). 1 C NMR (100.6 MHz, CDCl
3
J = 4.0 Hz, 1H), 2.57–2.41 (m, 2H), 2.39 (s, 1H).
C NMR
3
): d 145.9, 134.3, 133.8, 129.6,
(
3
100.6 MHz, CDCl ): d 149.0, 133.3, 132.2, 126.4, 119.5, 118.8,
27.6, 126.0, 123.9, 118.9, 72.5, 43.8. IR (KBr): 3389, 3082, 3010,
974, 2938, 2911, 1642, 1600, 1574, 1475, 1432, 1345, 1299,
1
2
9
11.2, 72.3, 43.8. IR (KBr): 3834, 3442, 3076, 2979, 2908, 2348,
229, 1928, 1840, 1642, 1609, 1572, 1504, 1415, 1303, 1056,
19, 872, 839, 759, 566 cm . MS (EI) m/z: [M] 173 (0.8), 132
ꢀ1
196, 1092, 1078, 1051, 918, 881, 785, 741, 695 cm . MS (EI) m/
ꢀ1
+
+
z: [M] 182 (0.7), 143 (29), 141 (89), 113 (45), 77 (100), 51 (18).
+
+
(
100), 104 (43), 77 (20). HRMS-EI (m/z): [M] calcd for C11H11NO,
HRMS-EI (m/z): [M] calcd for C10
82.0495. The enantioselectivity was measured by HPLC (Chiralcel
OD-H, 2-propanol/hexanes, 1:9, 0.25 mL/min) to be 78% ee.
H11ClO, 182.0498; found,
1
73.0841; found, 173.0836.
1
4
.2.18. Benzoic acid 1-(4-cyano-phenyl)-but-3-enyl ester 18a
1
4
.2.13. 1-(4-Chloro-phenyl)-but-3-en-1-ol 15
H NMR (400 MHz, CDCl
2H), 7.61–7.57 (m, 1H), 7.52–7.44 (m, 4H), 6.06–6.03 (m, 1H),
5.76–5.72 (m, 1H), 5.14–5.09 (m, 2H), 2.78–2.70 (m, 2H). 13
NMR (100.6 MHz, CDCl ): d 165.5, 145.4, 133.3, 132.3, 132.1,
3
): d 8.08–8.06 (m, 2H), 7.67–7.64 (m,
2
3:7
1
Yield: 75%. ½
CDCl ): d 7.31–7.25 (m, 4H), 5.81–5.70 (m, 1H), 5.16–5.11 (m,
H), 4.70–4.66 (m, 1H), 2.48–2.42 (m, 2H), 2.25 (s, 1H). C NMR
100.6 MHz, CDCl ): d 142.3, 133.9, 133.1, 128.5, 127.2, 118.7,
aꢁ
2 2
¼ þ43:6 (c 1.00, CH Cl ). H NMR (400 MHz,
D
C
3
1
3
2
(
3
129.8, 129.6, 128.5, 127.0, 119.0, 118.5, 111.8, 74.9, 40.6. IR
(KBr): 3063, 2925, 2857, 2345, 2229, 1974, 1924, 1714, 1645,
1601, 1451, 1335, 1318, 1269, 1173, 1108, 1065, 989, 921, 835,
3
7
1
6
1
1
2.5, 43.8. IR (KBr): 3389, 3077, 2992, 2907, 1641, 1596, 1492,
410, 1304, 1191, 1091, 1051, 1013, 918, 870, 830, 781, 647,
ꢀ
1
+
ꢀ1
+
24, 535 cm . MS (EI) m/z: [M] 182 (0.7), 143 (31), 141 (100),
712, 633, 563 cm . MS (EI) m/z: [M] 277 (0.4), 236 (8), 105
+
+
13 (19), 77 (69). HRMS-EI (m/z): [M] calcd for C10
H11ClO,
(100), 77 (23). HRMS-EI (m/z): [M] calcd for
18 2
C H15NO ,
82.0498; found, 182.0491.
277.1103; found, 277.1109. The enantioselectivity was measured

3
004
X.-R. Huang, C. Chen / Tetrahedron: Asymmetry 21 (2010) 2999–3004
by HPLC (Chiralcel OD-H, 2-propanol/hexanes, 1:9, 0.25 mL/min)
to be 47% ee.
J.; Hamilton, S. S.; Sigman, S. Org. Lett. 2005, 7, 1837–1839; (r) Xia, G.;
Yamamoto, H. J. Am. Chem. Soc. 2006, 128, 2554–2555; (s) Hargaden, G. C.;
O’Sullivan, T. P.; Guiry, P. J. Org. Biomol. Chem. 2008, 6, 562–566; (t) McManus,
H. A.; Cozzi, P. G.; Guiry, P. J. Adv. Synth. Catal. 2006, 348, 551–558; (u)
Hargaden, G. C.; Mueller-Bunz, H.; Guiry, P. J. Eur. J. Org. Chem. 2007, 4235–
Acknowledgement
4243; (v) Coeffard, V.; Aylward, M.; Guiry, P. J. Angew. Chem., Int. Ed. 2009, 48,
9
152–9155.
We are grateful for the generous financial support of the Na-
tional Science Council of the Republic of China (NSC 97-2113-M-
4
.
.
Asymmetric allylations not via a catalytic process: (a) Sugimoto, K.; Aoyagi, S.;
Kibayashi, C. J. Org. Chem. 1997, 62, 2322–2323; (b) Chen, C.; Tagami, K.; Kishi,
Y. J. Org. Chem. 1995, 60, 5386–5387; (c) Cazes, B.; Verniere, C.; Goré, J. Synth.
Commun. 1983, 13, 73–79.
(a) Casolari, S.; D’Addario, D.; Tagliavini, E. Org. Lett. 1999, 1, 1061–1063; (b)
Hamasaki, R.; Chounan, Y.; Horino, H.; Yamamoto, Y. Tetrahedron Lett. 2000, 41,
9
7
3
Org. Biomol. Chem. 2004, 2, 741–748; (f) Kim, J. G.; Waltz, K. M.; Garcia, I. F.;
Kwiatkowski, D.; Walsh, P. J. J. Am. Chem. Soc. 2004, 126, 12580–12585; (g) Teo,
Y.-C.; Goh, J.-D.; Loh, T.-P. Org. Lett. 2005, 7, 2743–2745; (h) Liu, L.-Y.; Tang, L.;
Yu, L.; Chang, W.-X.; Li, J. Tetrahedron 2005, 61, 10930–10934; (i) Lu, J.; Hong,
M.-L.; Ji, S.-J.; Teo, Y.-C.; Loh, T.-P. Chem. Commun. 2005, 4217–4218; (j)
Wooten, A. J.; Kim, J. G.; Walsh, P. J. Org. Lett. 2007, 9, 381–384.
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5
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