Page 7 of 10
The Journal of Organic Chemistry
41.1, 32,4, 25.4; MS (GCꢀEI, m/z) 232.1 (M); 96% ee [HPLC
126.1, 47.4, 41.9, 41.3, 31.4, 25.0; MS (GCꢀEI, m/z) 200.2 (M);
91% ee [HPLC conditions: Chiralcel ODꢀH column, hexane:
iPrOH = 98:2, flow rate 1.0 mL/min, wavelength = 249 nm, tR =
17.49 min for minor isomer, tR = 19.55 min for major isomer];
[α]25D –7.1 (c 1.0, CHCl3).
conditions: Chiralcel OJꢀH column, hexane: iPrOH = 97:3, flow
rate 0.8 mL/min, wavelength = 249 nm, tR = 90.63 min for
minor isomer, tR = 96.09 min for major isomer]; [α]23D +7.3 (c
0.9, CHCl3).
1
2
3
4
5
6
7
8
9
8c
7a,8a
(R)-3-(4-Acetylphenyl)cyclohexanone (7aN). The product
(R)-3-Phenylcyclopentanone (7bA).
The product was isoꢀ
was isolated by silica gel column chromatography (nꢀ
hexane/ethyl acetate = 5:1, Rf = 0.16) as a colorless oil (64.2
mg, 99% yield); 1H NMR (396 MHz, CDCl3, 20.3 °C)
J = 8.7 and 2.0 Hz, 2H), 7.32 (d, J = 8.3 Hz, 2H), 3.09 (tt, J =
11.5 and 3.6 Hz, 1H), 2.63–2.40 (m, 7H), 2.21–2.08 (m, 2H),
1.91–1.77 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3, 20.5 °C)
lated by silica gel column chromatography (nꢀhexane/ethyl
acetate = 5:1, Rf = 0.35) as a colorless oil (41.8 mg, 87% yield);
δ
7.94 (dt,
1H NMR (396 MHz, CDCl3, 19.6 °C)
δ 7.35 (t, J = 6.7 Hz, 2H),
7.27–7.26 (m, 3H), 3.43 (tt, J = 11.1 and 4.0 Hz, 1H), 2.67 (dd, J
= 18.2 and 7.9 Hz, 1H), 2.51–2.26 (m, 4H), 2.05–1.94 (m, 1H);
13C{1H} NMR (100 MHz, CDCl3, 19.5 °C)
δ 218.5, 143.0, 128.7,
δ
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
210.3, 197.6, 149.6, 135.7, 128.8, 126.8, 48.4, 44.6, 41.1, 32.4,
26.6, 25.4; MS (GCꢀEI, m/z) 216.1 (M); 95% ee [HPLC condiꢀ
tions: Chiralcel ADꢀH column, hexane: iPrOH = 9:1, flow rate
0.5 mL/min, wavelength = 249 nm, tR = 34.32 min for major
isomer, tR = 40.32 min for minor isomer]; [α]23D +14.7 (c 2.1,
CHCl3).
126.7, 45.8, 42.2, 38.9, 31.2; MS (GCꢀEI, m/z) 160.2 (M); 95%
ee [HPLC conditions: two Chiralcel ASꢀH columns, hexane:
iPrOH = 100:1, flow rate 0.5 mL/min, wavelength = 249 nm, tR
= 83.69 min for major isomer, tR = 97.96 min for minor isoꢀ
mer]; [α]23D +47.3 (c 1.01, CHCl3).
7a,8a
(R)-3-Phenylcycloheptanone (7cA).
The product was isoꢀ
22
(R)-3-(4-Cyanophenyl)cyclohexanone (7aO). The product
lated by silica gel column chromatography (nꢀhexane/ethyl
was isolated by silica gel column chromatography (nꢀ
acetate = 5:1, Rf = 0.55) as a colorless oil (33.3 mg, 59% yield);
1H NMR (396 MHz, CDCl3, 20.8 °C)
δ 7.31 (tt, J = 7.5 and 1.6
hexane/ethyl acetate = 5:1, Rf = 0.19) as a colorless oil (57.4 mg,
1
96% yield); H NMR (396 MHz, CDCl3, 20.4 °C)
δ
7.65 (dt, J =
Hz, 2H), 7.23–7.17 (m, 3H), 2.98–2.90 (m, 2H), 2.67–2.58 (m,
3H), 2.12–1.98 (m, 3H), 1.77–1.69 (m, 2H), 1.52–1.48 (m, 1H);
8.7 and 2.0 Hz, 2H), 7.36 (d, J = 8.7 Hz, 2H), 3.10 (tt, J = 11.9
13C{1H} NMR (100 MHz, CDCl3, 20.7 °C)
δ 213.6, 146.9, 128.6,
and 4.0 Hz, 1H), 2.63–2.39 (m, 4H), 2.21–2.09 (m, 2H), 1.90–
1.78 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3, 20.3 °C)
δ
209.8,
126.4, 126.3, 51.2, 43.9, 42.7, 39.2, 29,2, 24.2; MS (GCꢀEI, m/z)
188.1 (M); 89% ee [HPLC conditions: Chiralcel ODꢀH column,
hexane: iPrOH = 95:5, flow rate 0.5 mL/min, wavelength = 249
nm, tR = 16.95 min for minor isomer, tR = 18.20 min for major
isomer]; [α]25D +49.8 (c 0.6, CHCl3).
149.5, 132.5, 127.4, 118.7, 110.6, 48.1, 44.5, 40.9, 32.2, 25.2;
HRMS (GCꢀTOFꢀEI, m/z) calcd for C13H13NO (M) 199.0997,
found 199.0982; 97% ee [HPLC conditions: Chiralcel OJꢀH
column, hexane: iPrOH = 97:3, flow rate 1.0 mL/min, waveꢀ
length = 249 nm, tR = 66.62 min for minor isomer, tR = 70.05
min for major isomer]; [α]23D +1.8 (c 0.9, CHCl3).
8a
(R)-4-Phenyltetrahydro-2H-pyran-2-one (7dA). The prodꢀ
uct was isolated by silica gel column chromatography (nꢀ
8a
(R)-3-(1-Naphthyl)cyclohexanone (7aP). The product was
hexane/ethyl acetate = 5:1, Rf = 0.19) as a colorless oil (21.7 mg,
1
isolated by silica gel column chromatography (nꢀhexane/ethyl
41% yield); H NMR (396 MHz, CDCl3, 22.0 °C)
δ 7.37 (tt, J =
acetate = 5:1, Rf = 0.45) as a white solid (82.9 mg, 92% yield):
7.9 and 1.6 Hz, 2H), 7.28 (tt, J = 7.1 and 1.6 Hz, 1H), 7.21 (dt, J
= 7.1 and 1.6 Hz, 2H), 4.54–4.49 (m, 1H), 4.40 (td, J = 11.0 and
3.6 Hz, 1H), 3.25 (tt, J = 10.3 and 5.1 Hz, 1H), 2.93 (ddd, J =
17.0, 5.9, and 1.2m, 1H), 2.64 (dd, J = 17.8 and 10.3 Hz, 1H),
2.21–2.15 (m, 1H), 2.10–2.00 (m, 1H); 13C{1H} NMR (100 MHz,
mp 69–71°C; 1H NMR (396 MHz, CDCl3, 20.3 °C)
δ 8.02 (d, J =
8.3 Hz, 1 H), 7.86 (d, J = 7.5 Hz, 1 H), 7.74 (d, J = 7.5 Hz, 1 H),
7.54–7.37 (m, 4H), 3.84 (tt, J = 11.5 and 4.0 Hz, 1H), 2.78–2.40
(m, 4H), 2.24–2.15 (m, 2H), 2.04–1.87 (m, 2H); 13C{1H} NMR
(100 MHz, CDCl3, 19.9 °C)
δ
211.3, 140.0, 133.9, 130.8, 129.0,
CDCl3, 22.1 °C) δ 170.6, 142.7, 128.9, 127.1, 126.4, 68.6, 37.4,
127.2, 126.2, 125.6, 125.5, 122.6, 122.4, 48.5, 41.4, 39.3, 32.2,
25.5; MS (GCꢀEI, m/z) 224.2 (M); 84% ee [HPLC conditions:
Chiralcel ASꢀH column, hexane: iPrOH = 98:2, flow rate 1.0
mL/min, wavelength = 249 nm, tR = 12.62 min for major isoꢀ
37.3, 30.2; MS (GCꢀEI, m/z) 176.1 (M); 75% ee [HPLC condiꢀ
tions: Chiralcel ASꢀH column, hexane: iPrOH = 80:20, flow
rate 1.0 mL/min, wavelength = 249 nm, tR = 18.53 min for maꢀ
jor isomer, tR = 23.74 min for minor isomer]; [α]23D –0.9 (c 0.4,
CHCl3).
mer, tR = 21.23 min for minor isomer]; [α]24 +53.2 (c 1.4,
D
CHCl3).
(S)-1,3-Diphenylbutan-1-one (7eA).10aThe product was isoꢀ
lated by silica gel column chromatography (nꢀhexane/ethyl
7a,8a
(R)-3-(2-Naphthyl)cyclohexanone (7aQ).
The product
was isolated by silica gel column chromatography (nꢀ
acetate = 5:1, Rf = 0.35) as a colorless oil (55.2 mg, 82% yield);
1H NMR (396 MHz, CDCl3, 22.0 °C)
δ 7.92 (dt, J = 6.7 and 1.2
hexane/ethyl acetate = 5:1, Rf = 0.43) as a white solid (84.7 mg,
94% yield): mp 69–71 °C; 1H NMR (396 MHz, CDCl3, 19.9 °C)
δ
Hz, 2H), 7.54 (tt, J = 7.9 and 1.6 Hz, 1H), 7.44 (t, J = 7.9 Hz,
2H), 7.32–7.28 (m, 4H), 7.22–7.17 (m, 1H), 3.50 (sext, J = 7.10
Hz, 1H), 3.30 (dd, J = 17.0 and 5.9 Hz, 1H), 3.18 (dd, J = 17.0
and 8.3 Hz, 1H), 1.34 (d, J = 7.2 Hz, 3H); 13C{1H} NMR (100
7.82–7.79 (m, 3H), 7.64 (s, 1H), 7.50–7.46 (m, 2H), 7.36 (dd, J
= 7.9 and 1.6 Hz, 1H), 3.17 (tt, J = 11.1 and 7.5 Hz, 1H), 2.69–
2.60 (m, 2H), 2.51–2.37 (m, 2H), 2.21–2.14 (m, 2H), 2.00–1.78
(m, 2H); 13C{1H} NMR (100 MHz, CDCl3, 20.6 °C)
δ
211.0,
MHz, CDCl3, 22.0 °C) δ 199.0, 146.5, 137.1, 132.9, 128.5, 128.5,
141.7, 133.5, 132.3, 128.3, 127.6, 127.6, 126.2, 125.6, 125.3,
124.7, 48.8, 44.8, 41.2, 32.7, 25.5; MS (GCꢀEI, m/z) 224.1 (M);
95% ee [HPLC conditions: Chiralcel ASꢀH column, hexane:
iPrOH = 98:2, flow rate 1.0 mL/min, wavelength = 249 nm, tR =
22.49 min for major isomer, tR = 31.89 min for minor isomer];
[α]23D +47.3 (c 1.4, CHCl3).
128.0, 126.8, 126.2, 47.0, 35.5, 21.8; MS (GCꢀEI, m/z) 224.2
(M); 94% ee [HPLC conditions: Chiralcel ADꢀH column, hexꢀ
ane: iPrOH = 100:1, flow rate 0.5 mL/min, wavelength = 249
nm, tR = 18.49 min for major isomer, tR = 23.53 min for minor
isomer]; [α]23D +13.6 (c 1.1, CHCl3).
5a,7a
(R)-5-Methyl-4-phenylhexan-2-one (7fA).
The product
5b,7e
(R)-3-[(1E)-2-Phenylethenyl]cyclohexanone (7aR).
The
was isolated by silica gel column chromatography (nꢀ
product was isolated by silica gel column chromatography (nꢀ
hexane/ethyl acetate = 5:1, Rf = 0.69) as a colorless oil (42.2
mg, 74% yield); 1H NMR (396 MHz, CDCl3, 20.5 °C)
δ 7.27 (t, J
hexane/ethyl acetate = 5:1, Rf = 0.49) as a colorless oil (53.1 mg,
1
64% yield); H NMR (396 MHz, CDCl3, 20.5 °C)
δ
7.36–7.20
= 6.7 Hz, 2H), 7.17 (t, J = 7.5 Hz, 1H), 7.14 (d, J = 8.3 Hz, 2H),
2.92 (q, J = 5.9 Hz, 1H), 2.80–2.78 (m, 2H), 1.97 (s, 3H), 1.83
(sext, J = 7.1 Hz, 1H), 0.93 (d, J = 6.7 Hz, 3H), 0.74 (d, J = 7.1
(m, 5H), 6.39 (dd, J = 15.8 and 0.8 Hz, 1H), 6.16 (dd, J = 15.8
and 7.1, 1H), 2.69–2.66 (m, 1H), 2.56–2.50 (m, 1H), 2.44–2.37
(m, 1H), 2.36–2.28 (m, 2H), 2.11–2.07 (m, 1H), 2.05–1.99 (m,
1H), 1.78–1.68 (m 1H), 1.67–1.58 (m, 1H); 13C{1H} NMR (100
Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3, 20.5 °C)
143.2, 128.2, 128.1, 126.2, 48.0, 47.6, 33.3, 30.6, 20.7, 20.3; MS
δ 208.4,
MHz, CDCl3, 20.0 °C)
δ
210.9, 137.1, 132.9, 129.1, 128.6, 127.4,
(GCꢀEI, m/z) 190.2 (M); 96% ee [HPLC conditions: Chiralcel
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