Epoxide as an aldehyde equivalent in allyl-transfer reaction with γ-adduct of homoallylic alcohol (allyl donor) giving α-adduct of homoallylic alcohol

Article abstract of DOI:10.1016/j.tet.2007.02.130

Acid-catalyzed reactions of epoxides 2 with homoallylic alcohol γ-adducts, 1 [Me₂C(OH)CHRCH{double bond, long}CH₂], afford homoallylic alcohol α-adducts 3-5 via allyl-transfer reaction, sometimes being more effective than those using

Full text of DOI:10.1016/j.tet.2007.02.130

Tetrahedron 63 (2007) 9016–9022
Epoxide as an aldehyde equivalent in allyl-transfer reaction
with g-adduct of homoallylic alcohol (allyl donor)
giving a-adduct of homoallylic alcohol
*
Junzo Nokami, Kazuho Maruoka, Taichi Souda and Nobuo Tanaka
Department of Applied Chemistry, Okayama University of Science, 1-1 Ridai-cho, Okayama 700-0005, Japan
Received 29 January 2007; accepted 28 February 2007
Available online 9 June 2007
Abstract—Acid-catalyzed reactions of epoxides 2 with homoallylic alcohol g-adducts, 1 [Me C(OH)CHRCH]CH ], afford homoallylic
2
2
alcohol a-adducts 3–5 via allyl-transfer reaction, sometimes being more effective than those using the corresponding aldehydes.
Ó 2007 Elsevier Ltd. All rights reserved.
1
. Introduction
reaction conditions where 3b was obtained only in 58% yield
E/Z¼6.7/1) even for 20 h.
(
It is well known that epoxide serves as an aldehyde in the
presence of an acid catalyst as shown in Scheme 1. There-
fore, many reactions with aldehyde, such as allylation reac-
tion of aldehyde, have also been carried out with epoxide,
which is a synthetic equivalent of an aldehyde as shown in
1
This fact prompted us to study allyl-transfer reaction of 1a
4
,7
with easily available various epoxides 2. Typical results
are summarized in Table 2, although the reaction condi-
tions shown in Table 2 would not be suitable to give the
best result for all of the epoxides. It is noteworthy that vi-
nyl epoxide 2i gave the corresponding homoallylic alcohol
3i selectively and in good yield without any migration of
2
Scheme 2.
On the other hand, we have so far discovered a new allylation
reaction of aldehyde to give homoallylic alcohol a-adduct 3,
in which homoallylic alcohol g-adduct 1 served as an allyl
donor and transferred the allylic functionality into aldehyde
via stereospecific oxonia[3.3]-sigmatropic rearrangement as
6
the double bond (Scheme 5). Moreover, epoxides 2a,
2b, 2i, 2d–f, and 2h, which could give more stable interme-
diates T1 (Scheme 6), such as benzylic (entries 1 and 2),
allylic (entry 10), and tertiary (entries 4–7 and 9) cations
reacted with allyl donors more smoothly and gave better
yields than those (2c, 2g) giving less stable secondary cat-
ions (entries 3 and 8).
3
shown in Scheme 3.
Here we report an ‘allyl-transfer reaction’ of homoallylic
alcohol g-adduct 1 with epoxides, which are synthetic equiv-
alents of aldehydes (Scheme 4).
We also conducted allyl-transfer reaction with epoxides
using other allyl donors 1b, 1c (1b, R¼n-C H ; 1c,
5
11
8
R¼(CH ) Cl) and obtained the expected products in mod-
2
3
2
. Results and discussion
erate yields (Table 3).
First, we tried the reaction of 2,3-dimethyl-4-penten-2-ol 1a
with stilbene oxide 2b (R ¼R ¼Ph, R ¼H in Scheme 4)
In conclusion, we discovered that allyl-transfer reaction of
epoxides 2 took place with allyl donor, homoallylic alcohol
g-adduct 1, to give homoallylic alcohol a-adducts 3–5 in
a similar manner as the allylation of aldehydes, which are
synthetic equivalents of the corresponding epoxides 2. In
a few cases, however, the product yields were better than
those obtained from the corresponding aldehydes. This is
because the hemiacetal intermediate (T3) can be formed
directly from 2 via T1 and T2. That is, the formation of
T3 from T1 will be easier and faster than that from the cor-
responding aldehyde, which are unstable and sterically
1
2
3
4a
ꢀ
using an acid catalyst at 20 C for 5 h in CH Cl . Typical
2
2
results are listed in Table 1.
It seemed to be interesting for us that homoallylic alcohol
a-adduct 3b was obtained faster and in better yield (entry
7) than that in the allyl-transfer reaction of 1a with the cor-
responding aldehyde, 2,2-diphenylethanal, under similar
5
*
Corresponding author. E-mail: nogami@dac.ous.ac.jp
0
040–4020/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2007.02.130

J. Nokami et al. / Tetrahedron 63 (2007) 9016–9022
9017
R
Lewis Acid (LA)
R
H
R
R
H
O
-
LA
O H
O
O H
LA
LA
Scheme 1. Epoxide as an aldehyde equivalent.
allylic nucleophile
MX
Lewis Acid
(LA)
OH
R
R
R
R
O
O
O
LA
LA
Scheme 2. Allylation of epoxide as an aldehyde equivalent.
H
OH
H+
HO O
R'
O
O
R
- H2O
R
R
R'
R'
γ
+ R' CHO
aldehyde
α
R
oxonia[3.3]-sigmatropic
rearrangement
1
(1a, R = Me)
homoallylic alcohol γ-adduct)
(
H2O
α
(CH3)2CO, - H+
-
+ H2O
R'
O
R
R
R'
OH
homoallylic alcohol α-adduct)
3
(
Scheme 3. Allylation of aldehyde via allyl-transfer reaction.
OH
R2
R3
3. Experimental
3.1. General methods
Infrared spectra were recorded on a Nicolet Series II Magna-
O
O
acid catalyst
R3
+
2
R
+
R1
R
1
1a
2 (epoxide)
OH
3
Scheme 4. Allyl-transfer reaction with epoxides.
1
13
IR system 550 spectrometer. H NMR (400 MHz) and
C
NMR (100 MHz) spectra were measured on a JEOL
JNMX 400 spectrometer. High-resolution mass spectra
(HRMS) were obtained with a JEOL JMS-700 mass spectro-
meter. Elemental analyses were obtained on a Perkin–Elmer
PE-2400 Series II CHN analyzer. Dichloromethane was
dried over calcium hydride and distilled. Tetrahydrofuran
(THF) and diethyl ether were distilled from benzophenone
ketyl. All other chemical reagents were used as supplied
without further purification.
a
Table 1. Crotylation of stilbene oxide 2b via allyl-transfer reaction
b
Catalyst (mol %)
c
Yield of 3b (%)
d
Entry
E/Z
1
2
3
4
5
6
7
8
9
TSA$H O (5)
2
0
68
23
54
67
65
70
50
60
70
82
0
—
TfOH (5)
BF $OEt
Sc(OTf)
TMSOTf (5)
4.6/1
4.8/1
3.7/1
4.7/1
4.5/1
5.2/1
5.0/1
5.0/1
4.7/1
4.6/1
—
3
2
(5)
(5)
3
Sn(OTf)
2
(5)
(5)
(2)
(10)
In(OTf)
In(OTf)
In(OTf)
In(OTf)
In(OTf)
3
3
3.2. General procedure
3
3
3
10
11
12
13
14
(5) and TfOH (5)
(3) and TfOH (5)
(5)
3.2.1. Allyl-transfer reaction of 2,3-dimethyl-4-penten-2-
Bi(OTf)
Yb(OTf)
Er(OTf)
3
ol (1a) with styrene oxide (2a) to give 1-phenylhex-4-en-2-
ol (3a). To a stirred solution of 1a (57.1 mg, 0.5 mmol) and
styrene oxide 2a (58 ml, 0.5 mmol) in CH Cl (2 mL) was
3
(5)
(5)
0
Trace
—
—
3
2
2
a
Reactions were performed with 2,3-dimethyl-4-penten-2-ol (1a) and
ꢀ
added In(OTf) (14.1 mg, 0.025 mmol), and the reaction
3
stilbene oxide 2b in the presence of an acid catalyst at 20 C in CH
2
Cl
2
ꢀ
rated aqueous sodium bicarbonate (3 mL) was added to the
reaction mixture at 0 C. The resulting mixture was ex-
mixture was warmed to 40 C. After stirring for 6 h, satu-
for 5 h.
TSA (p-toluenesulfonic acid); TfOH (trifluoromethanesulfonic acid).
b
c
d
ꢀ
Isolated yield.
Determined by H NMR.
1
tracted with chloroform (3ꢁ2 mL). The combined extracts
were dried over anhydrous sodium sulfate, and concentrated
in vacuo. The residue was purified by column chromato-
graphy on silica gel (n-hexane/EtOAc¼20:1 to 3:1 as eluent)
to give 3a in 62% yield.
hindered (Scheme 6). It seems that the acid-catalyzed re-
action of epoxide (from 2 to T2) is faster than the following
allyl-transfer reaction (from T2 to 3–5), although the yield
of 3–5 largely depends on the stability and steric hindrance
of T1, T2, and T3.
3.2.1.1. Compound 3a. A mixture of E- and Z-isomers;
pale yellow oil; R 0.52 (n-hexane/EtOAc¼3/1); IR (neat)
f

9018
J. Nokami et al. / Tetrahedron 63 (2007) 9016–9022
a
Table 2. Crotylation of epoxides 2 with 1a via allyl-transfer reaction
b
ꢀ
b
Time, h
c
Entry
2
Temp,
C
% Yield of 3
1
2
R
3
d
E/Z
R
R
A
(B)
1
2
3
4
5
6
7
8
9
a
b
c
d
d
e
f
g
h
i
Ph
Ph
H
H
H
Me
Me
Et
Me
H
H
Ph
H
H
H
H
H
H
H
H
H
40 (20)
20 (20)
20
20 (20)
40
20 (20)
20 (20)
40
40 (20)
20 (20)
20 (20)
6 (15)
5 (5)
25
15 (15)
6
30 (20)
15 (12)
30
15 (20)
20 (15)
25 (20)
a
b
c
62
69
0
(84)
(82)
7.1/1
5.2/1
—
Ph(CH
Ph(CH
Ph(CH
Ph(CH
Me
2
2
2
2
)
)
)
)
2
2
2
2
e
e
d
d
55
62
50
78
31
49
46, 80
31
(61)
8.6/1
8.0/1
8.9/1
7/1
e
e
f
(52)
(80)
f
C
C
C
6
H
6
H
5
H
13
13
g
h
i
5.1/1
5.4/1
4.0/1
7.6/1
e
Me
H
(51)
(49)
(51)
g
10
1
11CH]CH
–(CH
1
j
2
)
5
–
j
a
Reactions were performed with 2,3-dimethyl-4-penten-2-ol (1a) (0.5 mmol) and epoxide 2 (0.5 mmol) in the presence of an acid catalyst A: In(OTf)
5 mol %) in CH Cl (2 mL) or B: In(OTf) (3 mol %) and TfOH (5 mol %) in CH Cl (4 mL), unless otherwise noted.
Reaction conditions corresponding to the yields in column B are shown in parentheses.
3
(
2
2
3
2
2
b
c
d
e
f
Isolated yield.
Determined by H NMR, unless otherwise noted.
1
13
Ca. 1:1 of diastereomeric mixture (determined by C NMR).
13
Determined by C NMR.
Performed with 2 equiv of epoxide 2i (1.0 mmol).
g
Lewis
O acid
3.2.1.2. 1,1-Diphenylhex-4-en-2-ol (3b). A mixture of
E- and Z-isomers; pale yellow oil; R 0.58 (n-hexane/
OLA
1a
OLA
f
C5H11
C5H11
C5H11
2i
EtOAc¼3:1); IR (neat) 3556, 3436, 3060, 3025, 2916,
H
ꢂ1
1
1
658, 1598, 1495, 1449, 1382, 973, 749, 702 cm ; H
C5H11
double bond migration
NMR (400 MHz, CDCl ) d 1.50 (br d, J¼5.6 Hz, 0.5H),
3
3i
OH
OLA
1
1
.68 (d, J¼3.6 Hz, 2.5H), 1.74 (br, 1H), 2.01–2.09 (m,
C5H11
H), 2.19–2.27 (m, 1H), 3.90 (E, d, J¼8.4 Hz, 0.84H),
Scheme 5. Allylation of b,g-unsaturated aldehyde equivalent 2i with 1a to
give 3i.
3.94 (d, J¼8.4 Hz, 0.16H), 4.37 (m, 1H), 5.45–5.53 (m,
1
3
2H), 7.15–7.42 (m, 10H); C NMR (E-isomer) (100 MHz,
CDCl ) d 18.1, 38.3, 57.8, 73.0, 126.4, 126.6, 126.9 (2),
3
1
1
28.2, 128.50 (2), 128.52, 128.6 (2), 128.7 (2), 141.4,
42.3. Anal. Calcd for C H O: C, 85.67; H, 7.99. Found:
C, 85.57; H, 8.02.
1
8 20
3
1
555, 3398, 3062, 3025, 2924, 1658, 1603, 1495, 1448,
076, 970, 743, 700 cm
ꢂ1
1
;
H
NMR (E-isomer)
(
400 MHz, CDCl ) d 1.68 (d, J¼3.6 Hz, 1H), 1.70 (d,
3.2.1.3. 3-Methyl-1-phenyloct-6-en-4-ol (3d). A mix-
ture of syn and anti, and E- and Z-isomers; colorless oil; Rf
0.56 (n-hexane/EtOAc¼3:1); IR (neat) 3404, 3026, 2962,
2932, 2879, 2858, 1605, 1496, 1453, 1378, 970, 748,
3
J¼6.0 Hz, 3H), 2.11–2.18 (m, 1H), 2.23–2.28 (m, 1H),
2
1
7
.72 (dd, J¼7.6, 13.2 Hz, 1H), 2.82 (dd, J¼5.2, 13.2 Hz,
H), 3.84 (m, 1H), 5.43–5.51 (m, 1H), 5.54–5.63 (m, 1H),
.21–7.25 (m, 3H), 7.29–7.33 (m, 2H); C NMR (E-isomer)
1
3
ꢂ1
1
699 cm ; H NMR (E-isomer) (400 MHz, CDCl ) d 0.97
3
(
100 MHz, CDCl ) d 18.1, 40.0, 43.2, 72.0, 126.3, 126.8,
3
and 0.99 (each d, J¼6.0, 6.4 Hz, resp., 3H), 1.4–1.7 (m,
6H), 1.69 (d, J¼6.0 Hz, 3H), 1.82 (m, 1H), 2.06 (m, 1H),
2.20 (m, 1H), 2.50–2.63 (m, 1H), 2.67–2.79 (m, 1H), 3.44
128.4 (2), 128.9, 129.3 (2), 138.5. Anal. Calcd for
C H O: C, 81.77; H, 9.15. Found: C, 81.65; H, 9.33.
1
2 16
R3
R2
OH
acid catalyst
O
2
R
R3
R
1
+
R
3, 4, 5
R1
OH
2
(epoxide)
R
O
1
1a, 3: R = CH3
Lewis acid
(allyl donor) 1b, 4: R = n-C5H11
1
+
H2O
R
(LA)
c, 5: R = (CH2)3Cl
R2 R3
R1
R2
OLA
3
R2 R3
R1
CHO
LA + LA
R
R1
O
T5
-
R2 R3
R1
R2 R3
R1
R2
R2 R3
1
OLA
- LAOH
OLA
R1
OLA
R1
HO
T3
O
R3
R
T2
R
T1
T4
Scheme 6. Allyl-transfer reaction with epoxides: a plausible reaction mechanism.

J. Nokami et al. / Tetrahedron 63 (2007) 9016–9022
9019
a
Table 3. Allyl-transfer reaction of epoxides 2 with allyl donor 1b, 1c
b
1
c
ꢀ
c
Time, h
d
Entry
2
Temp,
C
% Yield of 4, 5
1
R
2
3
R
e
R
A
(B)
E/Z
1
2
3
4
5
6
7
8
9
1b
1b
1b
1b
1b
1b
1c
1c
1c
1c
1c
1c
a
b
d
f
h
i
a
b
d
f
h
i
Ph
Ph
Ph(CH
Me
H
H
Me
Me
Me
H
H
H
Me
Me
Me
H
H
Ph
H
H
H
H
H
Ph
H
H
H
H
40 (20)
20 (20)
20 (20)
20 (20)
40
20 (20)
40
20
20
20
20
20
15 (10)
8 (3)
20 (20)
20 (13)
20
20 (20)
15
20
20
20
20
20
4a
4b
4d
4f
4h
4i
60
70
47
74
55
33
50
74
55
70
50
37
(54)
(81)
(56)
(81)
E
8/1
E
11/1
E
E
h
h
i
f
g
2
)
2
f
g
C
C
6
H
H
13
5
11CH]CH
(52)
Ph
Ph
Ph(CH
Me
5a
5b
5d
5f
5h
5i
E
5/1
26/1
12/1
26/1
E
g
2
)
2
f
10
11
12
g
C
C
6
H
H
13
i
5
11CH]CH
a
A: reactions were performed with allyl donor 1 (0.5 mmol) and epoxide 2 (0.5 mmol) in the presence of In(OTf)
presence of In(OTf) (3 mol %) and TfOH (5 mol %) in CH Cl (4 mL) unless otherwise noted.
Cl in Scheme 6.
3 2 2
(5 mol %) in CH Cl (2 mL) or B: in the
3
2
2
b
c
d
e
f
1b, R¼n-C
5
H
11; 1c, R¼(CH
2 3
)
Reaction conditions corresponding to the yields in column (B) are shown in parentheses.
Isolated yield.
1
Determined by H NMR of the products obtained in the system A, unless otherwise noted.
13
Determined by C NMR.
g
h
i
13
Ca. 1:1 of diastereomeric mixture (determined by C NMR).
3
Performed in the presence of TfOH (5 mol %) instead of In(OTf) .
Epoxide 2i (1.0 mmol) was used.
and 3.52 (each m, 0.4H and 0.6H, resp.), 5.41 (m, 1H), 5.55
(
(neat) 3361, 3018, 2926, 2858, 1658, 1458, 1375, 1125,
969 cm
1
3
ꢂ1
1
m, 1H), 7.15–7.30 (m, 5H); C NMR (E-isomer)
100 MHz, CDCl ) d 14.0 and 15.2, 18.11 and 18.12, 33.5
;
H NMR (400 MHz, CDCl ) d 0.88 (t, J¼
3
(
and 33.6, 34.1 and 35.1, 37.0 and 37.3, 37.72 and 37.73,
6.8 Hz, 3H), 1.29 (br, 10H), 1.44–1.49 (br m, 2H), 1.65 (br
d, J¼6.8 Hz, 0.5H), 1.70 (dd, J¼0.8, 6.4 Hz, 2.5H), 2.05
(dt, J¼7.6, 13.6 Hz, 1H), 2.19–2.27 (m, 1H), 3.54–3.62 (br
3
7
1
3.9 and 74.6, 125.5 (2), 127.5 and 127.6, 128.17 (4),
28.25 (4), 128.6 and 128.9, 142.58 and 142.6. Anal. Calcd
1
3
m, 1H), 5.39–5.48 (m, 1H), 5.51–5.61 (m, 1H); C NMR
for C H O: C, 82.52; H, 10.16. Found: C, 82.54; H, 10.52.
22
(E-isomer) (100 MHz, CDCl ) d 14.2, 18.2, 22.7, 25.8,
3
15
29.3, 29.7, 31.9, 36.8, 40.7, 71.0, 127.1, 128.9. HRMS (EI)
m/z calcd for C H O 184.1827. Found 184.1821.
3.2.1.4. 3-Ethyl-1-phenyloct-6-en-4-ol (3e). A mixture
of syn and anti, and E- and Z-isomers; colorless oil; Rf
1
2 24
0
2
.61 (n-hexane/EtOAc¼3:1); IR (neat) 3414, 3085, 3026,
3.2.1.7. 6-Methyldodec-2-en-5-ol (3h). A mixture of syn
and anti, and E- and Z-isomers; colorless oil; R 0.67 (n-
ꢂ1
933, 2875, 1604, 1496, 1454, 1378, 969, 748, 698 cm
;
f
1
H NMR (E-isomer) (400 MHz, CDCl ) d 0.93 (t, J¼
hexane/EtOAc¼3:1); IR (neat) 3380, 3021, 2926, 2856, 1457,
3
ꢂ1
1
7.2 Hz, 3H), 1.37–1.78 (m, 10H), 2.05–2.09 (m, 1H), 2.20
m, 1H), 2.57–2.71 (m, 2H), 3.63 (m, 1H), 5.41–5.44 (m,
1378, 968 cm ; H NMR (400 MHz, CDCl ) d 0.87–0.92
3
(
(m, 6H), 1.10–1.58 (m, 13H), 1.65 (Z, d, J¼6.8 Hz, 0.5H),
1.70 (E, d, J¼6.4 Hz, 2.5H), 1.99–2.11 (m, 1H), 2.17–2.25
(m, 1H), 3.40–3.42 (m, 0.4H), 3.46–3.49 (m, 0.6H), 5.43–
1
3
1
H), 5.52–5.57 (m, 1H), 7.16–7.30 (m, 5H); C NMR (E-
isomer) (100 MHz, CDCl ) d 11.65 and 11.67, 18.1 (2),
3
1
3
2
4
1
1
8
1.7 and 22.6, 30.8 and 31.5, 33.7 (2), 37.3 and 37.7,
3.98 and 44.04, 72.07 and 72.10, 125.53 and 125.55,
27.62 and 127.67, 128.18 (4), 128.24 (4), 128.79 and
28.84, 142.7 and 142.8. Anal. Calcd for C H O: C,
5.45 (m, 1H), 5.53–5.57 (m, 1H); C NMR (E-isomer)
(100 MHz, CDCl ) d 14.0 and 15.2, 14.2 (2), 18.12 and
3
18.13, 22.7 (2), 27.2 and 27.3, 29.66 and 29.68, 31.9 (2),
32.2 and 33.2, 36.9 and 37.77, 37.84 and 38.1, 74.2 and
74.7, 127.7 and 127.8, 128.5 and 128.8. Anal. Calcd for
C H O: C, 78.72; H, 13.21. Found: C, 78.95; H, 13.39.
1
6 24
2.70; H, 10.41. Found: C, 82.91; H, 10.42.
1
3 26
3
.2.1.5. 2-Methylhept-5-en-3-ol (3f). A mixture of
E- and Z-isomers; colorless oil; Rf 0.56 (n-hexane/
EtOAc¼3:1); IR (neat) 3371, 3019, 2960, 1655, 1462,
3.2.1.8. Trideca-2,7-dien-5-ol (3i). A mixture of 2E- and
2Z-isomers; pale yellow oil; R 0.60 (n-hexane/EtOAc¼3:1);
f
ꢂ1
1
ꢂ1 1
1
380, 971 cm ; H NMR (E-isomer) (400 MHz, CDCl )
3
IR (neat) 3393, 2928, 2858, 1457, 1377, 969 cm ; H NMR
d 0.93 (d, J¼6.4 and 9.2 Hz, 6H), 1.63–1.70 (m, 2H), 1.69
(400 MHz, CDCl ) d 0.88 (t, J¼7.0 Hz, 3H), 1.2–1.4 (m,
3
(
d, J¼5.2 Hz, 3H), 2.04 (dt, J¼8.0, 14.8 Hz, 1H), 2.20–
6H), 1.64 (Z, d, J¼7.2 Hz, 0.6H), 1.69 (E, d, J¼6.2 Hz,
2.4H), 2.01 (q, J¼6.8 Hz, 2H), 2.05–2.15 (m, 2H), 2.17–
2.26 (m, 2H), 3.59 (m, 1H), 5.35–5.49 (m, 2H), 5.50–5.60
2
5
.28 (m, 1H), 3.33 (ddd, J¼3.2, 5.2, 8.8 Hz, 1H), 5.40–
1
3
.48 (m, 1H), 5.52–5.59 (m, 1H); C NMR (E-isomer)
1
3
(
100 MHz, CDCl ) d 17.64, 18.1, 18.8, 33.0, 37.6, 75.6,
3
(m, 2H); C NMR (E-isomer) (100 MHz, CDCl ) d 14.1,
3
1
1
27.6, 128.6; (Z-isomer) (100 MHz, CDCl ) d 17.57, 18.1,
3
8.9, 33.1, 37.6, 76.2, 126.6, 127.0. Anal. Calcd for
18.1, 22.5, 29.1, 31.4, 32.7, 39.9, 40.0, 70.5, 125.6, 127.0,
128.4, 134.3. Anal. Calcd for C H O: C, 79.53; H,
12.32. Found: C, 79.55; H, 12.39.
1
3 24
C H O: C, 74.94; H, 12.58. Found: C, 75.06; H, 12.55.
8 16
3
.2.1.6. Dodec-2-en-5-ol (3g). A mixture of E- and Z-
3.2.1.9. 1-Cyclohexylpent-3-en-1-ol (3j). A mixture of
E- and Z-isomers; colorless oil; Rf 0.60 (n-hexane/
isomers; colorless oil; R 0.60 (n-hexane/EtOAc¼3:1); IR
f

9020
J. Nokami et al. / Tetrahedron 63 (2007) 9016–9022
EtOAc¼3:1); IR (neat) 3378, 3018, 2925, 2855, 1657, 1448,
37.6, 75.5, 126.1, 134.5; (Z-isomer) (100 MHz, CDCl3)
d 14.2, 17.6, 18.9, 27.4, 29.4, 31.5, 32.2, 33.04, 37.6, 76.1,
125.5, 133.3. HRMS (EI) m/z calcd for C H O 184.1827.
ꢂ1
088, 1065, 1031, 969 cm ; H NMR (400 MHz, CDCl )
3
1
1
d 0.95–1.40 (m, 7H), 1.63–1.90 (m, 5H), 1.64 (Z, d,
J¼7.2 Hz, 0.6H), 1.70 (E, d, J¼6.4 Hz, 2.4H), 2.04 (dt,
J¼8.4, 13.6 Hz, 1H), 2.21–2.29 (m, 1H), 3.33 (m, 1H),
1
2 24
Found 184.1789.
1
3
5
.39–5.48 (m, 1H), 5.52–5.60 (m, 1H); C NMR (E-isomer)
3.2.1.14. 7-Methylhexadec-10-en-8-ol (4h). A mixture
of syn and anti isomers; colorless oil; R 0.70 (n-hexane/
(
100 MHz, CDCl ) d 18.2, 26.2, 26.4, 26.6, 28.3, 29.1, 37.5,
3
f
4
H, 11.98. Found: C, 78.57; H, 12.06.
3.0, 75.0, 127.6, 128.8. Anal. Calcd for C H O: C, 78.51;
1
EtOAc¼3:1); IR (neat) 3377, 2955, 2925, 2858, 1461,
1 20
ꢂ1
1
1378, 973 cm ; H NMR (400 MHz, CDCl ) d 0.88 (t,
3
J¼6.8 Hz, 9H), 1.08–1.64 (m, 18H), 1.94–2.12 (m, 3H),
3
.2.1.10. 1-Phenyldec-4-en-2-ol (4a). Colorless oil; Rf
2.18–2.27 (br m, 1H), 3.40–3.48 (br, 1H), 5.38–5.44 (m,
1
3
0
3
7
6
7
1
1
7
.40 (n-hexane/EtOAc¼3:1); IR (neat) 3557, 3405, 3062,
1H), 5.51–5.57 (m, 1H); C NMR (100 MHz, CDCl3)
d 14.06 (2), 14.12, 14.17 (2), 15.3, 22.6 (2), 22.7 (2),
27.25, 27.35, 29.2 (2), 29.66, 29.70, 31.4 (2), 31.9 (2),
32.2, 32.68, 32.70, 33.2, 37.0, 37.7, 37.9, 38.1, 74.1, 74.6,
126.3, 126.4, 134.4, 134.7. Anal. Calcd for C H O: C,
027, 2925, 2857, 1665, 1603, 1495, 1454, 1381, 1074, 972,
ꢂ1
1
42, 700 cm ; H NMR (400 MHz, CDCl ) d 0.88 (t, J¼
3
.8 Hz, 3H), 1.2–1.4 (m, 6H), 1.73 (br, 1H), 2.03 (q, J¼
.2 Hz, 2H), 2.14 (dt, J¼6.8, 13.5 Hz, 1H), 2.20–2.30 (m,
H), 2.71 (dd, J¼7.6, 13.6 Hz, 1H), 2.80 (dd, J¼5.0, 13.6 Hz,
H), 3.82 (br, 1H), 5.41–5.48 (m, 1H), 5.51–5.60 (m, 1H),
1
7 34
80.24; H, 13.47. Found: C, 80.24; H, 13.25.
1
3
.20–7.26 (m, 3H), 7.27–7.32 (m, 2H); C NMR (100 MHz,
CDCl ) d 14.1, 22.6, 29.2, 31.4, 32.7, 40.1, 43.2, 72.0, 125.5,
3
26.3, 128.4 (2), 129.3 (2), 134.7, 138.5. HRMS (EI) m/z
calcd for C H O 232.1827. Found 232.1804.
3.2.1.15. Heptadeca-6,11-dien-9-ol (4i). Colorless oil;
R 0.67 (n-hexane/EtOAc¼3:1); IR (neat) 3398, 2926,
f
ꢂ1
1
1
2856, 1466, 1379, 971 cm ; H NMR (400 MHz, CDCl )
3
d 0.88 (t, J¼6.8 Hz, 6H), 1.29–1.40 (m, 12H), 1.77 (br,
1
6 24
1
H), 2.02 (q, J¼6.8 Hz, 4H), 2.07–2.15 (m, 2H), 2.18–
3.2.1.11. 1,1-Diphenyldec-4-en-2-ol (4b). A mixture of
E- and Z-isomers; pale yellow oil; R 0.65 (n-hexane/
2.25 (m, 2H), 3.59 (br m, 1H), 5.41 (dt, J¼6.8, 15.2 Hz,
1
3
2H), 5.53 (dt, J¼6.8, 15.2 Hz, 2H); C NMR (100 MHz,
f
EtOAc¼3:1); IR (neat) 3562, 3454, 3060, 3027, 2924,
CDCl ) d 14.1, 22.6, 29.2, 31.4, 32.7, 40.0, 70.5, 125.7,
3
2
7
3
2
857, 1662, 1598, 1494, 1452, 1381, 1064, 973, 752,
02 cm ; H NMR (400 MHz, CDCl ) d 0.84–0.89 (m,
134.3. Anal. Calcd for C H O: C, 80.88; H, 12.78. Found:
7 32
1
ꢂ1
1
C, 80.77; H, 12.67.
3
H), 1.24–1.38 (m, 6H), 1.77 (br, 1H), 1.88–2.09 (m, 3H),
.20–2.27 (m, 1H), 3.91 (E, d, J¼8.4 Hz, 0.9H), 3.94 (Z,
3.2.1.16. 8-Chloro-1-phenyloct-4-en-2-ol (5a). Color-
less oil; R 0.40 (n-hexane/EtOAc¼3:1); IR (neat) 3562,
d, J¼8.4 Hz, 0.1H), 4.35–4.37 (br m, 1H), 5.42–5.54 (m,
f
1
3
2
H), 7.19–7.40 (m, 10H); C NMR (E-isomer) (100 MHz,
CDCl ) d 14.1, 22.5, 29.1, 31.4, 32.7, 38.4, 57.8, 73.0,
3422, 3085, 3062, 3027, 2930, 2870, 2850, 1602, 1496,
1454, 1442, 1387, 972, 744, 701 cm ; H NMR (400 MHz,
ꢂ1 1
3
1
1
25.5, 126.4, 126.5, 128.2 (2), 128.45 (2), 128.48 (2),
28.7 (2), 134.5, 141.4, 142.3. Anal. Calcd for C H O:
C, 85.66; H, 9.15. Found: C, 85.88; H, 8.85.
CDCl ) d 1.85 (quint, J¼6.8 Hz, 2H), 2.14–2.33 (m, 4H),
3
2.71 (dd, J¼8.0, 13.6 Hz, 1H), 2.82 (dd, J¼4.8, 13.6 Hz,
1H), 3.54 (t, J¼6.4 Hz, 2H), 3.85 (m, 1H), 5.53 (m, 2H),
2
2 28
1
3
7
32.1, 40.0, 43.3, 44.4, 72.0, 126.4, 127.4, 128.5, 129.3,
.20–7.35 (m, 5H); C NMR (100 MHz, CDCl ) d 29.8,
3
3.2.1.12. 2-Methyl-1-phenyldodec-6-en-4-ol (4d). A
mixture of syn and anti isomers; colorless oil; R 0.69 (n-
132.1, 138.3. HRMS (EI) m/z calcd for C H OCl
14 19
f
hexane/EtOAc¼3:1); IR (neat) 3421, 3085, 3026, 2926,
238.1124. Found 238.1160.
ꢂ1
1
2
857, 1605, 1501, 1457, 1377, 970, 747, 698 cm ; H
NMR (400 MHz, CDCl ) d 0.88 (t, J¼7.2 Hz, 3H), 0.96
3.2.1.17. 8-Chloro-1,1-diphenyloct-4-en-2-ol (5b). A
mixture of E- and Z-isomers; colorless oil; R 0.50 (n-hex-
3
and 0.97 (each d, J¼7.2, 6.4 Hz, resp., 3H), 1.24–1.70 (m,
f
9
H), 1.75–1.90 (m, 1H), 1.97–2.13 (m, 3H), 2.15–2.27 (br
ane/EtOAc¼3:1); IR (neat) 3566, 3447, 3060, 3027, 2908,
ꢂ1
m, 1H), 2.50–2.64 (m, 1H), 2.65–2.70 (m, 1H), 3.42 and
.51 (each m, 1H), 5.37 (m, 1H), 5.53 (m, 1H), 7.14–7.22
2847, 1598, 1494, 1451, 1387, 973, 757, 746, 704 cm
H NMR (400 MHz, CDCl ) d 1.7–1.85 (m, 3H), 1.98–
;
1
3
3
1
3
(m, 3H), 7.23–7.29 (m, 2H); C NMR (100 MHz, CDCl3)
d 14.0 and 15.3, 14.1 (2), 22.5 (2), 29.2 (2), 31.4 (2), 32.64
and 32.66, 33.55 and 33.67, 34.1 and 35.1, 37.1 and 37.3,
2.20 (m, ca. 1H), 2.15 (q, J¼6.8 Hz, ca. 2H), 2.2–2.3 (m,
1H), 3.43 and 3.49 (each t, J¼6.4 Hz, ca. 0.3 and 1.7H,
resp.), 3.90 and 3.91 (d, J¼8.8 Hz, ca. 0.84 and 0.16H,
resp.), 4.34–4.39 (m, 1H), 5.35–5.58 (m, 2H), 7.15–7.38
3
1
7.7 and 37.8, 73.9 and 74.3, 125.5 (2), 126.1 and 126.2,
28.2 (4), 128.3 (4), 134.5 and 134.8, 142.60 and 142.64.
1
3
(m, 10H); C NMR (E-isomer) (100 MHz, CDCl ) d 29.7,
3
Anal. Calcd for C H O: C, 83.15; H, 11.02. Found: C,
9 30
32.1, 38.3, 44.4, 57.9, 73.1, 126.5, 126.7, 127.4, 128.2,
128.5, 128.6, 128.7, 131.8, 141.2; C NMR (Z-isomer)
100 MHz, CDCl ) d 24.5, 32.2, 32.9, 44.4, 58.0, 73.5,
1
1
3
8
3.20; H, 10.88.
(
3
3
.2.1.13. 2-Methylundec-5-en-3-ol (4f). A mixture of
126.5, 126.7, 127.4, 128.2 (2), 128.5 (2), 128.6 (2), 128.7
(2), 131.8, 141.2, 142.1. Anal. Calcd for C H ClO: C,
76.30; H, 7.36. Found: C, 76.26; H, 7.20.
E- and Z-isomers; colorless oil; Rf 0.63 (n-hexane/
EtOAc¼3:1); IR (neat) 3388, 2958, 2926, 2868, 1660,
20
23
ꢂ1
1
1
463, 1381, 973 cm
;
H NMR (400 MHz, CDCl )
3
d 0.88 (t, J¼7.2 Hz, 3H), 0.93 (dd, J¼6.8 Hz, 6H), 1.22–
.40 (m, 6H), 1.58 (br, 1H), 1.64–1.72 (m, 1H), 1.99–2.08
m, 3H), 2.18–2.29 (m, 1H), 3.33 (m, 1H), 5.37–5.45 (m,
3.2.1.18. 10-Chloro-3-methyl-1-phenyldec-6-en-4-ol
(5d). A mixture of syn and anti, and E- and Z-isomers; color-
1
(
less oil; R 0.50 (n-hexane/EtOAc¼3:1); IR (neat) 3420,
f
1
3
1H), 5.52–5.60 (m, 1H); C NMR (E-isomer) (100 MHz,
CDCl ) d 14.1, 17.7, 18.8, 22.5, 29.2, 31.4, 32.7, 32.97,
3085, 3062, 3026, 2932, 2873, 1603, 1496, 1455, 1378,
ꢂ1
973, 748, 699 cm ; H NMR (400 MHz, CDCl ) d 0.96
3
1
3

J. Nokami et al. / Tetrahedron 63 (2007) 9016–9022
9021
1
and 0.98 (each d, J¼6.8, 6.4 Hz, resp., 3H), 1.40–1.60 (m,
3.2.1.24. 2-Hexyloxirane (2g). Colorless oil; H NMR
(400 MHz, CDCl ) d 0.89 (t, J¼6.8 Hz, 3H), 1.23–1.59
3
H), 1.83 (quint, J¼6.8 Hz, 3H), 2.0–2.3 (m, 4H), 2.50–
3
2
.64 (m, 1H), 2.65–2.80 (m, 1H), 3.41–3.58 (m, 1H), 3.52
(m, 10H), 2.47 (dd, J¼3.2, 5.2 Hz, 1H), 2.75 (t, J¼4.6 Hz,
1
3
(
t, J¼6.8 Hz, 2H), 5.49 (m, 2H), 7.15–7.21 (m, 3H), 7.24–
1H), 2.88–2.94 (m, 1H); C NMR (100 MHz, CDCl )
3
1
3
7
d 13.9 and 15.3, 29.7 (2), 32.1 (2), 33.6 and 34.0, 35.1 and
.30 (m, 2H); C NMR (E-isomer) (100 MHz, CDCl )
d 14.1, 22.6, 26.0, 29.1, 31.8, 32.5, 47.1, 52.4.
3
3
1
1
8
7.0, 37.3 and 37.8, 44.4 (2), 74.0 and 74.7, 125.6 (2),
27.9 and 128.0, 128.2 (4), 128.3 (4), 131.9 and 132.1,
42.5 and 142.6. Anal. Calcd for C H ClO: C, 72.71; H,
3.2.1.25. 2-Hexyl-2-methyloxirane (2h). Colorless oil;
H NMR (400 MHz, CDCl ) d 0.88 (t, J¼6.8 Hz, 3H),
1
3
1.23–1.63 (m, 10H), 1.31 (s, 3H), 2.59 (dd, J¼4.8,
1
7 25
1
3
.97. Found: C, 72.67; H, 8.73.
14.8 Hz, 1H); C NMR (100 MHz, CDCl ) d 14.1, 20.9,
3
22.6, 25.2, 29.3, 31.8, 36.7, 53.9, 57.0.
3
.2.1.19. 9-Chloro-2-methylnon-5-en-3-ol (5f). A mix-
ture of E- and Z-isomers; colorless oil; R 0.53 (n-hexane/
1
3.2.1.26. 2-(1-Heptenyl)oxirane (2i). Colorless oil; H
f
EtOAc¼3:1); IR (neat) 3413, 2946, 2936, 2876, 1471,
NMR (400 MHz, CDCl ) d 0.89 (t, J¼6.8 Hz, 3H), 1.23–
3
ꢂ1
1
1
446, 1387, 972 cm
;
H NMR (400 MHz, CDCl )
3
1.45 (m, 6H), 2.07 (q, J¼6.8 Hz, 2H), 2.65 (dd, J¼2.8,
4.8 Hz, 1H), 2.94 (t, J¼4.8 Hz, 1H), 3.32 (dq, J¼2.8,
8.4 Hz, 1H), 5.13 (dd, J¼8.4, 15.2 Hz, 1H), 5.96 (dt,
d 0.92 (d, J¼6.4 Hz, 3H), 0.93 (d, J¼6.4 Hz, 3H), 1.51 (br,
1
2
H), 1.67 (oct, J¼6.4 Hz, 1H), 1.85 (quint, J¼6.8 Hz, 2H),
1
3
.06 (br m, 1H), 2.12–2.30 (br m, 3H), 3.35 (br, 1H), 3.54
J¼6.8, 15.2 Hz, 1H); C NMR (100 MHz, CDCl ) d 14.0,
3
1
3
(
t, J¼6.4 Hz, 2H), 5.50 (br, 2H); C NMR (E-isomer)
22.5, 28.6, 31.3, 32.3, 48.8, 52.5, 127.3, 137.2.
(
100 MHz, CDCl ) d 17.5, 18.76, 29.7, 32.1, 33.0, 37.5,
3
1
3
44.3, 75.6, 128.0, 131.8; C NMR (Z-isomer) (100 MHz,
CDCl ) d 18.84, 24.5, 32.2, 32.3, 33.2, 37.5, 44.4, 76.2,
3
Acknowledgements
1
27.5, 130.6. Anal. Calcd for C H ClO: C, 62.98; H,
10 19
1
0.04. Found: C, 62.86; H, 10.02.
.2.1.20. 1-Chloro-8-methyltetradec-4-en-7-ol (5h). A
mixture of syn and anti, and E- and Z-isomers; colorless
This work was financially supported by the Okayama Foun-
dation for Science and Technology.
3
oil; R 0.67 (n-hexane/EtOAc¼3:1); IR (neat) 3393, 2928,
f
ꢂ1
1
2
856, 1458, 1378, 972 cm
;
H NMR (E-isomer)
References and notes
(
400 MHz, CDCl ) d 0.85–0.92 (m, 6H), 1.10–1.65 (m,
3
1
2H), 1.85 (quint, J¼6.8 Hz, 2H), 2.00–2.28 (m, 4H), 3.43
1. (a) House, H. O. J. Am. Chem. Soc. 1955, 77, 3070–3075; (b)
Maruoka, K.; Murase, N.; Bureau, R.; Ooi, T.; Yamamoto, H.
Tetrahedron 1994, 50, 3663–3672; (c) Ishihara, K.; Hanaki, N.;
Yamamoto, H. Synlett 1995, 721–722; (d) Kulasegaram, S.;
Kulawiec, R. J. J. Org. Chem. 1994, 59, 7195–7196; (e)
Takanami, T.; Hirabe, R.; Ueno, M.; Hino, F.; Suda, K. Chem.
Lett. 1996, 1031–1032; (f) Suda, K.; Baba, K.; Nakajima, S.;
Takanami, T. Tetrahedron Lett. 1999, 40, 7243–7246; (g) Suda,
K.; Kikkawa, T.; Nakajima, S.; Takanami, T. J. Am. Chem. Soc.
2004, 126, 9554–9555; (h) Ranu, B. C.; Jana, U. J. Org. Chem.
1998, 63, 8212–8216; (i) Procopio, A.; Dalpozzo, R.; Nino, A.;
Nardi, M.; Sindona, G.; Tagarelli, A. Synlett 2004, 2633–2635.
2. (a) Lautens, M.; Ouellet, S. G.; Raeppel, S. Angew. Chem., Int.
Ed. 2000, 39, 4079–4082; (b) Lautens, M.; Maddess, M. L.;
Sauer, E. L. O.; Ouellet, S. G. Org. Lett. 2002, 4, 83–86; (c)
Yadav, J. S.; Anjaneyulu, S.; Ahmed, M. M.; Reddy, B. V. S.
Tetrahedron Lett. 2001, 42, 2557–2559; (d) Yadav, J. S.;
Reddy, B. V. S.; Satheesh, G. Tetrahedron Lett. 2003, 44,
6501–6504; (e) Oh, B. K.; Cha, J. H.; Cho, Y. S.; Choi, K. I.;
Koh, H. Y.; Chan, M. H.; Pae, A. N. Tetrahedron Lett. 2003,
(
m, 1H), 3.49 (m, 1H), 3.54 (t, J¼6.4 Hz, 2H), 5.50 (m,
1
3
2
1
2
3
1
6
H); C NMR (E-isomer) (100 MHz, CDCl ) d 13.9 and
3
5.2, 14.2 (2), 22.7 (2), 27.2 and 27.3, 29.6 and 29.7,
9.75 and 29.77, 31.9 (2), 32.1 (2), 33.2 (2), 36.9 and
7.78, 37.85 and 38.2, 44.4 (2), 74.2 and 74.8, 128.2 and
28.3, 131.7 and 132.0. Anal. Calcd for C H ClO: C,
1
5 29
9.07; H, 11.21. Found: C, 69.10; H, 11.15.
3
.2.1.21. 1-Chloropentadeca-4,9-dien-7-ol (5i). Color-
less oil; R 0.53 (n-hexane/EtOAc¼3:1); IR (neat) 3405,
f
ꢂ1
1
2
927, 2872, 1441, 1379, 971 cm ; H NMR (400 MHz,
CDCl ) d 0.88 (t, J¼6.8 Hz, 3H), 1.15–1.40 (m, 7H), 1.73
3
(
2
br, 1H), 1.84 (quint, J¼6.8 Hz, 2H), 2.02 (q, J¼6.8 Hz,
H), 2.05–2.27 (m, 5H), 3.54 (t, J¼6.4 Hz, 2H), 3.61 (br
m, 1H), 5.40 (dt, J¼6.8, 15.2 Hz, 1H), 5.47–5.58 (m, 3H);
1
3
C NMR (100 MHz, CDCl ) d 14.1, 22.6, 29.2, 29.8,
3
3
1.4, 32.2, 32.7, 39.9, 40.1, 44.4, 70.4, 125.5, 127.5,
31.7, 134.6. HRMS (EI) m/z calcd for C H O 258.1750.
1
Found 258.1733.
1
5 27
4
Araki, S. Tetrahedron Lett. 2004, 45, 9189–9191.
4, 2911–2913; (f) Hirashita, T.; Mitsui, K.; Hayashi, Y.;
3.2.1.22. 2-(2-Phenylethyl)oxirane (2c). Colorless oil;
H NMR (400 MHz, CDCl ) d 1.38 (s, 3H), 1.78–1.94 (m,
1
3. (a) Nokami, J.; Yoshizane, K.; Matsuura, H.; Sumida, S. J. Am.
Chem. Soc. 1998, 120, 6609–6610; (b) Sumida, S.; Ohga, M.;
Mitani, J.; Nokami, J. J. Am. Chem. Soc. 2000, 122, 1310–
1313; (c) Nokami, J.; Anthony, L.; Sumida, S. Chem.—Eur. J.
2000, 6, 2909–2913; (d) Nokami, J.; Ohga, M.; Nakamoto, H.;
Matsubara, T.; Hussain, I.; Kataoka, K. J. Am. Chem. Soc.
2001, 123, 9168–9169; (e) Hussain, I.; Komasaka, T.; Ohga,
M.; Nokami, J. Synlett 2002, 640–642; (f) Nokami, J.;
Nomiyama, K.; Matsuda, S.; Imai, N.; Kataoka, K. Angew.
Chem., Int. Ed. 2003, 42, 1273–1275; (g) Nokami, J.;
Nomiyama, K.; Shafi, S. M.; Kataoka, K. Org. Lett. 2004, 6,
3
2
2
H), 2.48 (dd, J¼2.8, 4.8 Hz, 2H), 2.71–2.87 (m, 3H),
1
3
.92–2.99 (m, 1H), 7.15–7.35 (m, 5H);
C NMR
(
100 MHz, CDCl ) d 32.2, 34.3, 47.2, 51.7, 125.9, 128.2,
3
1
28.3, 141.1.
.2.1.23. 2-(2-Phenylethyl)-2-methyloxirane (2d). Col-
orless oil; H NMR (400 MHz, CDCl ) d 1.38 (s, 3H), 1.79–
3
1
3
1
7
3
.97 (m, 2H), 2.59 (q, J¼5.2 Hz, 2H), 2.66–2.78 (m, 2H),
1
3
.17–7.31 (m, 5H); C NMR (100 MHz, CDCl ) d 21.0,
3
1.4, 38.5, 53.9, 56.6, 125.8, 128.1, 128.3, 141.4.

9022
J. Nokami et al. / Tetrahedron 63 (2007) 9016–9022
1
261–1264; (h) Shafi, S. M.; Chou, S.; Kataoka, K.; Nokami, J.
6. In connection with this fact, we would like to add the following
separate experimental results. Epoxide 2i (0.5 mmol) was
Org. Lett. 2005, 7, 2957–2960; Loh et al. also reported allyl-
transfer reaction, (i) Loh, T.-P.; Hu, q.-y.; Ma, L.-T. J. Am.
Chem. Soc. 2001, 123, 2450–2451; (j) Lee, C.-L. K.; Lee,
C.-H. A.; Tan, K.-T.; Loh, T.-P. Org. Lett. 2004, 6, 1281–1283;
McDonald et al. used allyl-transfer reaction for their highly
stereoselective synthetic reactions, (k) Wiseman, J. M.;
McDonald, F. E.; Liotta, D. C. Org. Lett. 2005, 7, 3155–3157;
ꢀ
treated with 3 mol % of Er(OTf)
3
in dichloromethane at 20 C
1
1
i
for 1 h to give non-3-enal. The H NMR spectrum clearly
showed that non-3-enal was produced as a single olefinic alde-
hyde (ca. 50%) together with much of impurities, which may
be less polar saturated hydrocarbonic compounds. Treatment
of this crude non-3-enal with 1a (0.5 mmol) in the presence of
(
4
l) Chen, Y.-H.; McDonald, F. E. J. Am. Chem. Soc. 2006, 128,
568–4569.
3
In(OTf) (5 mol %) gave 3i selectively in 45% isolated yield
based on epoxide 2i. This result clearly shows that allyl-transfer
reaction giving 3i surely occurs also via an intermediate alde-
hyde, and also that the direct reaction of epoxide 2i with 1a is
much effective (46% yield; see Table 2, entry 10). It is notewor-
4
. (a) Epoxides 2b and 2f were commercially available; (b)
Epoxides 2d, 2e, 2h and 2j were prepared according to
Corey’s method using dimethyloxosulfonium methylide from
the corresponding ketones. Corey, E. J.; Chaykovsky, M.
J. Am. Chem. Soc. 1965, 87, 1353–1364; (c) Preparation of 2i
was performed according to the method reported by Lautens
et al. via epoxidation of epichlorohydrin, 1-chloronon-3-en-2-ol,
prepared by a nucleophilic chloromethylation (using chloro-
7
methyllithium) of 2-octenal; (d) Epoxidation of alkenes was
thy that treatment of 2i with 3 mol % of In(OTf) gave only
3
3
a trace of non-3-enal, although Er(OTf) is ineffective for
allyl-transfer reaction. This clearly shows an unstability of
non-3-enal and a usefulness of such a tandem reaction.
7. Sadhu, K. M.; Matteson, D. S. Tetrahedron Lett. 1986, 27, 795–
798.
2b
performed with m-CPBA to give 2a, 2c, and 2g.
. 2,2-Diphenylethanal was prepared from stilbene oxide 2b in
8. Allyl donors 1a–c were prepared from acetone by allylation with
the corresponding Grignard reagents (for 1a, 1b) and by
Reformatsky reaction with 1-bromo-6-chlorohex-2-ene and
zinc (for 1c), see Ref. 3f.
5
62% isolated yield by treatment with In(OTf)
CH
3
(3 mol %) in
ꢀ
2
Cl
2
at 20 C for 30 min.