27
mmol); (R)-1 (10.0 mM in acetone, 2.50 mL, 25.0 µmol); 24 h.
13.7 min (major), 14.6 min (minor). [α]D +46.3 (c 1.00,
SiO -chromatography (10 g, 10:1 hexane–EtOAc eluent) to give
CHCl3).
2
4
5
-(4-(trifluoromethyl)phenyl)hex-5-en-2-one (3e) (63.0 mg,
1
5.4.8. 4-Thiophen-2-ylhex-5-en-2-one (3i)
2% yield, 99:1 er). H NMR (CDCl ) δ 2.11 (s, 3H, CH ), 2.84
3
3
(E)-3-Thiophen-2-ylprop-2-en-1-yl 3-oxobutanoate (2i) (500
(dd, J = 16.9 and 6.89 Hz, 1H, CHH), 2.92 (dd, J = 16.9 and
mM in CH Cl , 1.00 mL, 112 mg, 0.500 mmol); 24 h. SiO -
2
2
2
6
1
1
8
.89 Hz, 1H, CHH), 4.00 (q, J = 6.89 Hz, 1H, CH), 5.03 (d, J =
7.2 Hz, 1H, =CHH), 5.10 (d, J = 10.3 Hz, 1H, =CHH), 5.91 (m,
chromatography (10 g, 10:1 hexane–EtOAc eluent) to give 4-
thiophen-2-ylhex-5-en-2-one (3i) (85.6 mg, 95% yield, >99:1
H, CH=CH ), 7.33 (d, J = 7.57 Hz, 2H, aromatic), 7.56 (d, J =
2
1
er). H NMR (CDCl ) δ 2.14 (s, 3H, CH ), 2.85–2.94 (m, 2H,
3
3
.26 Hz, 2H, aromatic). HPLC condition: CHIRALPAK AS-H
CH ), 4.21 (q, J = 7.57 Hz, 1H, CH), 5.09 (d, J = 10.3 Hz, 1H,
2
(0.46 cmφ x 25 cm); hexane–2-propanol 99:1 eluent, 0.5
=
CHH), 5.10 (d, J = 16.5 Hz, 1H, =CHH), 5.92–5.99 (m, 1H,
mL/min; 230 nm light; t , 10.5 min (minor), 13.1 min (major).
R
27
1
CH=CH ), 6.83 (d, J = 3.44 Hz, 1H, aromatic), 6.93 (dd, J =
2
[
α]D –5.15 (c 0.50, CHCl3). H-NMR data were consistent
4
.82 and 3.44 Hz, 1H, aromatic), 7.16 (d, J = 4.82 Hz, 1H,
with reported values [20].
13
aromatic). C NMR (CDCl ) δ 30.7, 39.8, 49.8, 115.3, 123.7,
3
5
.4.5. 4-(N-Boc-pyrrol-2-yl)hex-5-en-2-one (3f)
E)-3-(N-Boc-pyrrol-2-yl)prop-2-en-1-yl 3-oxobutanoate (2f)
500 mM in CH Cl , 1.00 mL, 154 mg, 0.500 mmol); 6 h. SiO -
1
24.0, 126.8, 139.9, 146.4, 206.4. HRMS (ESI) m/z: calcd for
+
(
C H NaO S [M+Na] , 203.0501; found, 203.0562. HPLC
10 12 2
(
condition: CHIRALPAK IB (0.46 cmφ x 25 cm); hexane–2-
2
2
2
chromatography (10 g, 10:1 hexane–EtOAc eluent) to give 4-(N-
Boc-pyrrol-2-yl)hex-5-en-2-one (3f) (125 mg, 95% yield, >99:1
propanol 99:1 eluent, 0.5 mL/min; 220 nm light; t , 16.8 min
R
25
(major), 17.8 min (minor). [α]D +15.8 (c 1.00, CHCl3).
.4.9. 5-Phenylhept-6-en-3-one (3n)
E)-3-Phenylprop-2-en-1-yl 3-oxopentanoate (2n) (500 mM
1
er). H NMR (CDCl ) δ 1.59 (s, 9H, C(CH ) ), 2.16 (s, 3H,
3
3 3
5
CH ), 2.73 (dd, J = 16.2 and 8.26 Hz, 1H, CHH), 2.89 (dd, J =
3
(
1
4
1
6.2 and 6.20 Hz, 1H, CHH), 4.68 (q, J = 6.20 Hz, 1H, CH),
.92 (dt, J = 17.2 and 1.38 Hz, 1H, =CHH), 5.03 (d, J = 10.3 Hz,
in CH Cl , 1.00 mL, 116 mg, 0.500 mmol); 18 h. SiO2-
2
2
chromatography (10 g, 10:1 hexane–EtOAc eluent) to give 5-
H, =CHH), 5.95–6.02 (m, 2H, CH=CH and aromatic), 6.08 (t,
2
1
phenylhept-6-en-3-one (3n) (83.8 mg, 89% yield, >99:1 er).
H
J = 3.44 Hz, 1H, aromatic), 7.20 (dd, J = 3.44 and 2.07 Hz, 1H,
13
NMR (CDCl ) δ 0.98 (t, J = 7.57 Hz, 3H, CH CH ), 2.26–2.35
3
2
3
aromatic).
C NMR (CDCl ) δ 28.0, 30.0, 36.9, 48.6, 83.7,
3
(
m, 1H, CHHCH ), 2.35–2.44 (m, 1H, CHHCH ), 2.79 (dd, J =
3
3
1
09.8, 111.0, 114.7, 121.6, 136.3, 139.5, 149.2, 207.0. HRMS
+
16.2 and 7.57 Hz, 1H, CHH), 2.86 (dd, J = 15.8 and 7.57 Hz,
(ESI) m/z: calcd for C H NNaO [M+Na] , 286.1414; found,
15 21 3
1
1
H, CHH), 3.93 (q, J = 6.89 Hz, 1H, CH), 5.02 (d, J = 17.2 Hz,
H, =CHH), 5.05 (d, J = 10.3 Hz, 1H, =CHH), 5.93–6.00 (m,
2
86.1446. HPLC condition: CHIRALPAK IB (0.46 cmφ x 25
cm); hexane–2-propanol 99:1 eluent, 0.5 mL/min; 254 nm light;
25
1H, CH=CH ), 7.18–7.23 (m, 3H, aromatic), 7.30 (t, J = 7.57
2
tR, 12.3 min (major), 13.5 min (minor). [α]D –0.291 (c 1.00,
Hz, 2H, aromatic). HPLC condition: CHIRALPAK ID-3 (0.46
CHCl3).
cmφ x 25 cm); hexane–2-propanol 99:1 eluent, 0.5 mL/min; 254
2
4
5
.4.6. N-Boc-4-indol-3-ylhex-5-en-2-one (3g)
E)-3-(N-Boc-indol-3-yl)prop-2-en-1-yl 3-oxobutanoate (2g)
500 mM in CH Cl , 1.00 mL, 179 mg, 0.500 mmol); 6 h. SiO -
nm light; t , 13.3 min (minor), 14.3 min (major). [α] –22.6 (c
R
D
1
(
0.50, CHCl3). H-NMR data were consistent with reported
values [20].
(
2
2
2
chromatography (10 g, 10:1 hexane–EtOAc eluent) to give N-
Boc-4-indol-3-ylhex-5-en-2-one (3g) (125 mg, 80% yield, 99:1
5
.4.10. 2-Methyl-5-phenyhept-6-en-3-one (3o)
(E)-3-Phenylprop-2-en-1-yl 4-methyl-3-oxopentanoate (2o)
1
er). H NMR (CDCl ) δ 1.67 (s, 9H, C(CH ) ), 2.16 (s, 3H,
3
3 3
(500 mM in CH Cl , 1.00 mL, 123 mg, 0.500 mmol); 18 h.
2 2
CH ), 2.90–3.00 (m, 2H, CH ), 4.17 (q, J = 6.89 Hz, 1H, CH),
3
2
SiO -chromatography (10 g, 15:1 hexane–EtOAc eluent) to give
2
5
=
.10 (d, J = 9.64 Hz, 1H, =CHH), 5.12 (d, J = 17.2 Hz, 1H,
CHH), 5.96–6.03 (m, 1H, CH=CH ), 7.23 (t, J = 7.57 Hz, 1H,
2
9
1
-methyl-5-phenylhept-6-en-3-one (3o) (70.8 mg, 70% yield,
2
1
9:1 er). H NMR (CDCl ) δ 0.97 (d, J = 6.87 Hz, 3H, CH ),
3
3
aromatic), 7.31 (t, J = 7.57 Hz, 1H, aromatic), 7.37 (br, 1H,
aromatic), 7.56 (d, J = 7.57 Hz, 1H, aromatic), 8.12 (br, 1H,
.04 (d, J = 6.87 Hz, 3H, CH ), 2.46–2.54 (m, 1H, CH(CH ) ),
3
3 2
13
2.84 (dd, J = 16.2 and 7.57 Hz, 1H, CHH), 2.89 (dd, J = 16.5
and 6.87 Hz, 1H, CHH), 3.95 (q, J = 6.87 Hz, 1H, CH), 5.01 (d,
J = 17.2 Hz, 1H, =CHH), 5.05 (d, J = 10.3 Hz, 1H, =CHH),
aromatic).
C NMR (CDCl ) δ 28.2, 30.6, 35.7, 47.9, 83.6,
3
1
1
15.3, 115.4, 119.6, 121.9, 122.3, 122.4, 124.4, 129.4, 135.7,
39.1, 149.7, 206.8. HRMS (ESI) m/z: calcd for C H NNaO
19
23
3
+
5.94–6.01 (m, 1H, CH=CH ), 7.18–7.21 (m, 3H, aromatic), 7.29
2
[
M+Na] , 336.1570; found, 336.1563.
HPLC condition:
(t, J = 7.56 Hz, 2H, aromatic). HPLC condition: CHIRALPAK
CHIRALPAK IG (0.46 cmφ x 25 cm); hexane–2-propanol 99:1
IE-3 (0.46 cmφ x 25 cm); hexane–2-propanol 99:1 eluent, 0.5
mL/min; 220 nm light; t , 14.6 min (minor), 15.3 min (major).
eluent, 0.4 mL/min; 254 nm light; t , 23.1 min (minor), 28.4 min
R
25
R
(
m
a
j
o
r
)
.
[
α
]
+
2
8
.
1
(
c
1
.
0
0
,
C
H
C
l
)
.
D
3
25
1
[
α]D –17.6 (c 1.01, CHCl3). H-NMR data were consistent
5
.4.7. 4-Furan-2-ylhex-5-en-2-one (3h)
E)-3-Furan-2-ylprop-2-en-1-yl 3-oxobutanoate (2h) (500
mM in CH Cl , 1.00 mL, 104 mg, 0.500 mmol); 24 h. SiO -
with reported values [27].
(
5
.4.11. 2,2-Dimethyl-5-phenylhept-6-en-3-one (3p)
E)-3-Phenylprop-2-en-1-yl 4,4-dimethyl-3-oxopentanoate
2p) (500 mM in CH Cl , 1.00 mL, 130 mg, 0.500 mmol); 18 h.
2
2
2
(
chromatography (10 g, 15:1 hexane–EtOAc eluent) to give 4-
(
2
2
furan-2-ylhex-5-en-2-one (3h) (73.9 mg, 90% yield, >99:1 er).
1
SiO -chromatography (10 g, 20:1 hexane–EtOAc eluent) to give
2
yield, 99:1 er). H NMR (CDCl ) δ 1.05 (s, 9H, C(CH ) ), 2.85–
2
1
2
H NMR (CDCl ) δ 2.14 (s, 3H, CH ), 2.77 (dd, J = 16.5 and
3
3
,2-dimethyl-5-phenylhept-6-en-3-one (3p) (44.3 mg, 41%
1
7
4
5
6
.57 Hz, 1H, CHH), 2.93 (dd, J = 16.5 and 6.89 Hz, 1H, CHH),
.01 (q, J = 6.89 Hz, 1H, CH), 5.09 (d, J = 17.2 Hz, 1H, =CHH),
.11 (d, J = 9.64 Hz, 1H, =CHH), 5.85–5.92 (m, 1H, CH=CH2),
.03 (d, J = 2.75 Hz, 1H, aromatic), 6.29 (s, 1H, aromatic), 7.32
3
3 3
.95 (m, 2H, CH ), 3.99 (q, J = 6.89 Hz, 1H, CH), 5.01 (d, J =
2
7.2 Hz, 1H, =CHH), 5.04 (d, J = 10.3 Hz, 1H, =CHH), 5.94–
13
6.01 (m, 1H, CH=CH ), 7.17–7.23 (m, 3H, aromatic), 7.29 (t, J
2
13
(s, 1H, aromatic). C NMR (CDCl ) δ 30.4, 38.4, 46.8, 105.3,
3
=
7.57 Hz, 2H, aromatic). C NMR (CDCl ) δ 26.1, 42.3, 44.0,
3
1
10.2, 116.1, 137.6, 141.4, 155.6, 206.4. HRMS (ESI) m/z:
+
44.1, 114.4, 126.4, 127.8, 128.5, 140.9, 143.4, 213.4. HRMS
calcd for C H NaO [M+Na] , 187.0730; found, 187.0728.
10
12
2
+
(ESI) m/z: calcd for C H NaO [M+Na] , 239.1406; found,
15 20
HPLC condition: CHIRALPAK IB (0.46 cmφ x 25 cm);
hexane–2-propanol 99:1 eluent, 0.5 mL/min; 254 nm light; tR,
2
39.1408. HPLC condition: CHIRALPAK IE-3 (0.46 cmφ x 25