6352
Y. Kita et al. / Tetrahedron 71 (2015) 6349e6353
J¼14.2, 4.8, 3.4 Hz, 1H), 3.79 (dd, J¼7.7, 5.7 Hz, 1H), 3.73 (ddd,
J¼14.2, 11.7, 4.2 Hz, 1H), 3.16 (m, 1H), 3.10 (td, J¼11.7, 4.8 Hz, 1H),
5.18e5.01 (m, 2H), 3.00 (dd, J¼7.8, 4.5 Hz, 2H), 2.76 (m,1H), 2.55 (m,
13
1H), 2.36e2.16 (m, 2H), 1.87 (m, 1H). C NMR (126 MHz, CDCl
199.5,144.2,136.4,133.3,132.8,128.8,127.7,126.8,116.9, 47.4, 34.2,
28.8, 28.2. IR (Neat Film, NaCl) 3073, 2976, 2929, 1686, 1682, 1640,
3
)
13
2
.76 (m, 1H), 2.35 (m, 1H). C NMR (126 MHz, CDCl
3
)
d
173.2, 171.6,
d
1
35.6, 134.1, 132.0, 128.2, 128.1, 118.1, 43.6, 42.2, 33.3, 26.9. IR (Neat
Film, NaCl) 3362, 3065, 2933, 1687, 1600, 1580, 1534, 1450, 1378,
ꢁ1
1600, 1455, 1435, 1359, 1293, 1280, 1220, 1156 cm . HRMS (ESI/
ꢁ1
þ
1
326, 1281, 1177, 1132, 1071, 1026 cm . HRMS (FABþ) m/z calcd for
APCIþ) m/z calcd for C13
H
15O [MþH] : 187.1117, found 187.1110. SFC
þ
C
5
14
H
16NO
2
S [MþH] : 262.0902, found 262.0895. SFC conditions:
conditions: 0.5% MeCN, 3.0 mL/min, Chiralcel OD-H column,
¼254 nm, t (min): major¼8.11, minor¼7.74.
% MeOH, 3.0 mL/min, Chiralcel OD-H column,
l
¼254 nm, t
R
(min):
l
R
major¼9.26, minor¼8.79.
4
.2.8. 2-Methyl-1-phenylpent-4-en-1-one (9b). Reaction performed
ꢀ
4
.2.4. 3-Allyl-1-benzoylazepan-2-one (4d). Reaction performed in
in toluene at 23 C. Compound 9b was isolated by flash chroma-
tography (SiO , 0e3% EtOAc in hexanes) as a colorless oil. Quant.
¼0.43 (10% EtOAc in hexanes). 81% ee, [
ꢀ
toluene at 40 C. Compound 4d was isolated by flash chromatog-
2
2
5
raphy (SiO
2
, 10% EtOAc in hexanes) as a yellow oil. 83% yield.
R
f
a]
D
ꢁ32.9 (c 0.50, CH
8.02e7.97 (m, 2H), 7.60 (m, 1H),
7.55e7.47 (m, 2H), 5.83 (m, 1H), 5.14e5.02 (m, 2H), 3.60 (m, 1H),
2 2
Cl ).
2
5
1
R
f
¼0.44 (17% EtOAc in hexanes). 85% ee, [
a
]
D
ꢁ33.9 (c 1.90, CHCl
) 7.55e7.49 (m, 2H), 7.46 (m, 1H),
.40e7.34 (m, 2H), 5.78 (m, 1H), 5.11e5.03 (m, 2H), 4.56 (dd, J¼14.8,
.8 Hz, 1H), 3.44 (ddd, J¼14.8, 10.7, 0.9 Hz, 1H), 2.83 (m, 1H), 2.55
3
).
3
H NMR (500 MHz, CDCl ) d
1
H NMR (500 MHz, CDCl
7
5
3
13
2.61 (m, 1H), 2.25 (m, 1H),1.26 (d, J¼6.9 Hz, 3H). C NMR (126 MHz,
CDCl 203.6, 136.4, 135.8, 132.9, 128.7, 128.3, 116.8, 40.4, 37.6, 17.0.
IR (Neat Film, NaCl) 3077, 2975, 2933, 2358, 1682, 1641, 1596, 1579,
3
) d
13
(
(
4
2
m, 1H), 2.12e1.96 (m, 3H), 1.90 (m, 1H), 1.74e1.44 (m, 3H). C NMR
126 MHz, CDCl 178.7, 174.5, 136.8, 136.2, 131.4, 128.1, 127.7, 117.1,
5.9, 44.5, 36.4, 30.2, 28.8, 28.7. IR (Neat Film, NaCl) 3073, 3030,
931, 2857, 1681, 1641, 1600, 1583, 1513, 1490, 1450, 1396, 1360,
ꢁ
1
3
)
d
1447, 1374, 1360, 1239, 1209 cm . HRMS (ESI/APCIþ) m/z calcd for
þ
C
12
H
15O [MþH] : 175.1117, found 175.1113. SFC conditions: 0.5%
MeCN, 3.0 mL/min, Chiralcel OD-H column,
major¼3.97, minor¼4.42.
l¼254 nm, t
R
(min):
ꢁ
1
1322, 1282, 1220, 1189, 1177, 1141, 1114, 1044, 1018, 1001 cm
.
þ
HRMS (ESIþ) m/z calcd for C16
H20NO
2
[MþH] : 258.1489, found
2
58.1494. SFC conditions: 5% MeOH, 3.0 mL/min, Chiralcel AD-H
Acknowledgements
column,
l
¼254 nm, t
R
(min): major¼4.48, minor¼4.88.
The authors wish to thank NIH-NIGMS (R01GM080269), Amgen,
the Gordon and Betty Moore Foundation, the Caltech Center for
Catalysis and Chemical Synthesis, and Caltech for financial support.
Y.K. expresses his special thanks to the International Engineering
Science Consortium for financial support. Y.N. thanks Toray In-
dustries Inc. for a postdoctoral fellowship. N.O. is grateful for
a postdoctoral fellowship provided by Hiroshima International
University. The authors thank Scott Virgil (Caltech) for in-
strumentation assistance and Dr. Douglas C. Behenna (Caltech) for
initial experimental results.
4
.2.5. 3-Allyl-1-benzoylazocan-2-one (4e). Reaction performed in
ꢀ
toluene at 23 C. Compound 4e was isolated by flash chromatog-
raphy (SiO , 10% EtOAc in hexanes) as a yellow oil. 84% yield.
¼0.50 (17% EtOAc in hexanes). 59% ee, [
2
2
5
R
f
a
]
D
ꢁ8.6 (c 0.37, CHCl
7.56e7.22 (m, 5H), 5.80 (ddt, J¼17.2,
0.5, 6.9 Hz, 1H), 5.18e5.02 (m, 2H), 4.19 (ddd, J¼15.1, 4.3, 3.0 Hz,
3
).
1
3
H NMR (300 MHz, CDCl ) d
1
1
2
H), 3.85 (ddd, J¼15.1, 12.6, 2.8 Hz, 1H), 3.01 (m, 1H), 2.53 (m, 1H),
13
.21e2.05 (m, 2H), 1.92e1.70 (m, 4H), 1.70e1.35 (m, 3H). C NMR
180.7, 174.9, 136.8, 136.1, 131.3, 128.1, 127.9, 117.4,
(
126 MHz, CDCl
3
)
d
4
2
5.1, 44.0, 38.0, 36.7, 31.2, 25.9, 24.5. IR (Neat Film, NaCl) 3067,
928, 2857, 1679, 1619, 1493, 1448, 1392, 1319, 1285, 1246, 1176,
Supplementary data
ꢁ1
þ
1
125, 1091 cm . HRMS (ESIþ) m/z calcd for C17
H22NO
2
[MþH] :
272.1645, found 272.1656. SFC conditions: 5% MeOH, 3.0 mL/min,
Chiralcel OJ-H column,
minor¼3.87.
l¼254 nm,
t
R
(min): major¼2.97,
References and notes
4.2.6. 1-Benzoyl-3-(2-chloroallyl)azepan-2-one (4f). Reaction per-
ꢀ
formed in toluene at 23 C. Compound 4f was isolated by flash
chromatography (SiO , 15% EtOAc in hexanes) as a yellow oil. 42%
yield. R
¼0.37 (17% EtOAc in hexanes). 91% ee, [
2
2
5
f
1
a
]
D
ꢁ78.1 (c 1.20,
7.56e7.50 (m, 2H), 7.46 (m, 1H),
.41e7.29 (m, 2H), 5.26 (d, J¼1.2 Hz, 1H), 5.19 (d, J¼1.2 Hz, 1H), 4.58
3 3
CHCl ). H NMR (500 MHz, CDCl ) d
7
2
3
(
dd, J¼15.1, 5.1 Hz, 1H), 3.50 (dd, J¼15.1, 11.0 Hz, 1H), 3.23 (m, 1H),
2
2
.85 (ddd, J¼14.6, 6.4, 1.0 Hz, 1H), 2.32 (ddd, J¼14.6, 7.7, 0.7 Hz, 1H),
13
.15e1.99 (m, 2H), 1.89 (m, 1H), 1.78e1.55 (m, 2H), 1.48 (m, 1H).
C
3
NMR (126 MHz, CDCl ) d
178.0,174.5,140.0,136.7,131.6,128.2,127.9,
1
2
15.5, 44.7, 43.5, 41.6, 29.6, 28.9, 28.7. IR (Neat Film, NaCl) 2931,
857, 1683, 1636, 1450, 1397, 1358, 1321, 1274, 1220, 1188, 1148,
ꢁ1
þ
1
126 cm . HRMS (ESIþ) m/z calcd for C16
H
19ClNO
2
[MþH] :
2
92.1099, found 292.1104. SFC conditions: 5% MeOH, 3.0 mL/min,
6
Chiralcel OD-H column,
minor¼4.97.
l¼254 nm,
t
R
(min): major¼5.89,
4
.2.7. 2-Allyl-3,4-dihydronaphthalen-1(2H)-one (9a). Reaction per-
ꢀ
formed in toluene at 40 C. Compound 9a was isolated by flash
chromatography (SiO , 0e3% EtOAc in hexanes) as a pale colorless
oil. 91% yield. R
¼0.40 (9% EtOAc in hexanes). 90% ee, [
). H NMR (300 MHz, CDCl
8.04 (dd, J¼7.9, 1.5 Hz, 1H),
.46 (td, J¼7.5, 1.5 Hz, 1H), 7.36e7.16 (m, 2H), 5.95e5.75 (m, 1H),
2
2
5
f
a]
D
þ26.6 (c
1
0
7
.61, CHCl
3
3
) d