The Journal of Organic Chemistry
Note
(sept, JH,H = 6.96 Hz, 1H), 2.39 (s, 3H), 1.20 (d, JH,H = 6.96 Hz, 6H).
13C{1H} NMR (100 MHz, CDCl3): δ 204.3, 143.7, 133.8, 129.4,
128.6, 35.3, 21.7, 19.4. IR (KBr): νCO 1682 cm−1. GC−MS (M+):
162.1.
128.4, 40.7, 33.6, 29.8, 22.9, 17.4, 14.1. IR (KBr): νCO 1736 cm−1.
GC−MS (M+): 190.2.
3-Methoxy-13,16-dimethyl-7,8,9,11,12,13,15,16-octahydro-6H-
cyclopenta-phenanthren-17-(14H)-one (9).50 The compound was
prepared from estrone methyl ether (114 mg, 0.4 mmol) following
general procedure P. The title product was isolated by column
chromatography (n-hexane/EtOAc: 19:1) and obtained as a colorless
dense liquid (57 mg, 81% isolated yield). 1H NMR (400 MHz,
CDCl3): δ 7.20 (d, JH,H = 8.48 Hz, 1H), 6.72 (dd, JH,H = 8.56, 2.68
Hz, 1H), 6.64 (d, JH,H = 2.68 Hz, 1H), 2.91−2.84 (m, 2H), 2.40−2.13
(m, 3H), 2.02−1.89 (m, 2H), 1.68−1.30 (m, 7H), 1.24 (d, JH,H = 7.08
Hz, 3H), 0.86 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 223.3,
222.8, 157.7, 137.9, 132.3, 126.4, 114.0, 111.7, 55.3, 49.2, 48.7, 48.5,
47.8, 44.3, 44.2, 44.2, 43.9, 39.4, 38.4, 38.1, 32.1, 32.0, 30.8, 30.1,
29.8, 26.9, 26.6, 26.0, 17.1, 16.8, 14.6, 14.3. IR (KBr): νCO 1736 cm−1.
GC−MS (M+): 298.2.
1-(4-Methoxyphenyl)-2-methylpropan-1-one (3).21 The com-
pound was prepared from 1-(4-methoxyphenyl)propan-1-one (65
mg, 0.4 mmol) and 1-(4-methoxyphenyl)ethanone (60 mg, 0.4
mmol) following general procedure P. The title product was isolated
by column chromatography (n-hexane/EtOAc: 49:1) and obtained as
a light yellow oil (63 mg, 89% isolated yield from 1-(4-
methoxyphenyl)propan-1-one; 60 mg, 85% isolated yield from 1-(4-
1
methoxyphenyl)ethanone). H NMR (400 MHz, CDCl3): δ 7.95 (d,
J
H,H = 9.08 Hz, 2H), 6.94 (d, JH,H = 8.96 Hz, 2H), 3.85 (s, 3H), 3.52
(sept, JH,H = 7.00 Hz, 1H), 1.20 (d, JH,H = 7.04 Hz, 6H). 13C{1H}
NMR (100 MHz, CDCl3): δ 203.3, 163.4, 130.7, 129.3, 113.9, 55.6,
35.1, 19.4. IR (KBr): νCO 1674 cm−1. GC−MS (M+): 178.1.
1-Mesityl-2-methylpropan-1-one (10).33 The compound was
prepared from 1-mesityl-2-methylpropan-1-one (65 mg, 0.4 mmol)
following general procedure P. The title product was isolated by
column chromatography (n-hexane/EtOAc: 19:1) and obtained as a
colorless oil (64 mg, 84% isolated yield). 1H NMR (400 MHz,
CDCl3): δ 6.82 (s, 2H), 2.98 (sept, JH,H = 7.00 Hz, 1H), 2.27 (s, 3H),
2.18 (s, 3H), 1.17 (d, JH,H = 7.12 Hz, 6H). 13C{1H} NMR (100 MHz,
CDCl3): δ 214.5, 139.2, 138.4, 133.3, 128.7, 42.3, 21.1, 19.7, 18.1. IR
(KBr): νCO 1694 cm−1. GC−MS (M+): 190.2.
1-(2-Methoxyphenyl)-2-methylpropan-1-one (4).21 The com-
pound was prepared from 1-(2-methoxyphenyl)-propan-1-one (65
mg, 0.4 mmol) and 1-(2-methoxyphenyl)ethanone (60 mg, 0.4
mmol) following general procedure P. The title product was isolated
by column chromatography (n-hexane/EtOAc: 49:1) and obtained as
a colorless oil (67 mg, 95% isolated yield from 1-(2-methoxyphenyl)-
1
propan-1-one; 65 mg, 92% from 1-(2-methoxyphenyl)ethanone). H
NMR (400 MHz, CDCl3): δ 7.50 (dd, JH,H = 7.60, 1.68 Hz, 1H), 7.42
(td, JH,H = 8.24, 1.72 Hz, 1H), 6.99 (t, JH,H = 7.36 Hz, 1H), 6.94 (d,,
JH,H = 8.32 Hz, 1H), 3.86 (s, 3H), 3.48 (sept, JH,H = 6.80 Hz, 1H),
1.14 (d, JH,H = 6.84 Hz, 6H). 13C{1H} NMR (100 MHz, CDCl3): δ
208.3, 157.8, 132.7, 130.1, 129.2, 120.8, 111.4, 55.6, 40.2, 18.7. IR
(KBr): νCO 1681 cm−1. GC−MS (M+): 178.1.
2-Methyl-1-(naphthalen-2-yl)propan-1-one (11).21 The com-
pound was prepared from 1-(naphthalen-2-yl)ethanone (68 mg, 0.4
mmol) following general procedure P. The title product was isolated
by column chromatography (n-hexane/EtOAc: 19:1) and obtained as
a white solid (67 mg, 85% isolated yield). For a 6 mmol scale, the
reaction isolated yield was 75% (0.89 g). 1H NMR (500 MHz,
CDCl3): δ 8.46 (s, 1H), 8.03 (dd, JH,H = 8.60, 1.65 Hz, 1H), 7.96 (d,
JH,H = 8.00 Hz, 1H), 7.90−7.86 (m, 2H), 7.60−7.52 (m, 2H), 3.73
(sept, JH,H = 6.85 Hz, 1H), 1.28 (d, JH,H = 6.85 Hz, 6H). 13C{1H}
NMR (125 MHz, CDCl3): δ 204.6, 135.7, 133.7, 132.8, 129.8, 129.7,
128.6, 128.4, 127.9, 126.8, 124.5, 35.6, 19.5. IR (KBr): νCO 1678
cm−1. GC−MS (M+): 198.2.
2-Methyl-3,4-dihydronaphthalen-1(2H)-one (5).24 The com-
pound was prepared from 3,4-dihydronaphthalen-1(2H)-one (58
mg, 0.4 mmol) following general procedure P. The title product was
isolated by column chromatography (n-hexane/EtOAc: 19:1) and
obtained as a colorless oil (62 mg, 96% isolated yield). For a 6 mmol
1
scale reaction, the isolated yield was 88% (0.84 g). H NMR (400
MHz, CDCl3): δ 8.03 (dd, JH,H = 7.88, 1.00 Hz, 1H), 7.46 (td, JH,H
=
2,4-Dimethyl-1-phenylpentan-3-one (12).20 The compound was
prepared from 4-phenylbutan-2-one (59 mg, 0.4 mmol) following
general procedure P. The title product was isolated by column
chromatography (n-hexane/EtOAc: 19:1) and obtained as a colorless
7.44, 1.32 Hz, 1H), 7.28 (t, JH,H = 7.64 Hz, 1H), 7.23 (d, JH,H = 7.72
Hz, 1H), 3.03−2.97 (m, 2H), 2.61−2.55 (m, 1H), 2.21−2.16 (m,
1H), 1.92−1.82 (m, 1H), 1.27 (d, JH,H = 6.72 Hz, 6H). 13C{1H}
NMR (100 MHz, CDCl3): δ 201.0, 144.3, 133.2, 132.5, 128.8, 127.5,
126.7, 42.8, 31.5, 29.0, 15.6. IR (KBr): νCO 1683 cm−1. GC−MS
(M+): 160.1.
1
oil (68 mg, 90% isolated yield). H NMR (500 MHz, CDCl3): δ
7.26−7.23 (m, 2H), 7.18−7.15 (m, 1H), 7.13 (d, JH,H = 7.05 Hz, 2H),
3.00−2.92 (m, 2H), 2.56−2.48 (m, 2H), 1.08 (d, JH,H = 6.70 Hz, 3H),
1.01 (d, JH,H = 6.95 Hz, 3H), 0.87 (d, JH,H = 6.85 Hz, 3H). 13C{1H}
NMR (125 MHz, CDCl3): δ 217.9, 140.2, 129.2, 128.5, 126.3, 46.7,
40.5, 39.7, 18.2, 17.9, 17.3. IR (KBr): νCO 1711 cm−1. GC−MS (M+):
190.2.
1-Benzo-(1,3)-dioxol-5-yl-2,4-dimethylpentan-3-one (13). The
compound was prepared from 4-benzo-(1,3)-dioxol-5-yl-butan-2-one
(77 mg, 0.4 mmol) following general procedure P. The title product
was isolated by column chromatography (n-hexane/EtOAc: 19:1) and
obtained as a colorless oil (88 mg, 94% isolated yield). 1H NMR (500
MHz, CDCl3): δ 6.69 (d, JH,H = 7.85 Hz, 1H), 6.61 (s, 1H), 6.56 (dd,
JH,H = 7.90, 1.25 Hz, 1H), 5.89 (d, JH,H = 0.90 Hz, 2H), 2.95−2.82
(m, 2H), 2.54−2.43 (m, 2H), 1.05 (d, JH,H = 7.85 Hz, 3H), 1.01 (d,
JH,H = 0.85 Hz, 3H), 0.89 (d, JH,H = 6.85 Hz, 3H). 13C{1H} NMR
(125 MHz, CDCl3): δ 217.9, 147.6, 146.0, 133.9, 122.0, 109.5, 108.2,
100.9, 46.8, 40.6, 39.4, 18.1, 17.9, 17.2. IR (KBr): νCO 1709 cm−1.
GC−MS (M+): 234.2. HRMS (ESI-TOF): calcd for C14H19O3 [M +
H]+, 235.1329; found, 235.1331.
2,6-Dimethylcyclohexanone (6).24 The compound was prepared
from cyclohexanone (39 mg, 0.4 mmol) following general procedure
P. The title product was isolated by column chromatography (n-
hexane/EtOAc: 49:1) and obtained as a colorless oil (24 mg, 48%
1
isolated yield). H NMR (400 MHz, CDCl3): δ 2.60−2.32 (m, 2H),
2.10−1.88 (m, 2H), 1.82−1.68 (m, 2H), 1.59−1.27 (m, 2H), 1.00 (d,
JH,H = 6.36 Hz, 3H). 13C{1H} NMR (125 MHz, CDCl3): δ 217.5,
214.8, 45.5, 42.8, 37.4, 34.9, 25.7, 20.3, 16.1, 14.7. IR (KBr): νCO
1710 cm−1. GC−MS (M+): 126.1.
2,4-Diphenylpentan-3-one (7).21 The compound was prepared
from 1,3-diphenylpropan-2-one (84 mg, 0.4 mmol) following general
procedure P. The title product was isolated by column chromatog-
raphy (n-hexane/EtOAc: 19:1) and obtained as a colorless oil (40 mg,
1
42% isolated yield). H NMR (400 MHz, CDCl3): δ 7.35−7.30 (m,
4H), 7.28−7.24 (m, 2H, including CDCl3 peak), 7.17−7.14 (m, 4H),
3.78 (q, JH,H = 6.92 Hz, 2H), 1.25 (d, JH,H = 7.12 Hz, 6H). 13C{1H}
NMR (100 MHz, CDCl3): δ 210.5, 141.1, 129.2, 128.1, 127.3, 51.0,
18.2. IR (KBr): νCO 1714 cm−1. GC−MS (M+): 238.1.
2-Methyl-1-phenylhexan-1-one (8).25 The compound was pre-
pared from 1-phenylhexan-1-one (70 mg, 0.4 mmol) following general
procedure P. The title product was isolated by column chromatog-
raphy (n-hexane/EtOAc: 19:1) and obtained as a colorless oil (61 mg,
2-Methyl-1-(9-methyl-9H-fluoren-2-yl)propan-1-one (14). The
compound was prepared from 1-(9H-fluoren-2-yl)ethanone (83 mg,
0.4 mmol) following general procedure P. The title product was
isolated by column chromatography (n-hexane/EtOAc: 19:1) and
obtained as a colorless oil (80 mg, 80% isolated yield). 1H NMR (400
MHz, CDCl3): δ 8.11 (s, 1H), 8.00 (dd, JH,H = 7.96, 1.28 Hz, 1H),
7.81−7.79 (m, 2H), 7.54−7.53 (m, 1H), 7.41−7.36 (m, 2H), 4.00 (q,
1
80% isolated yield). H NMR (400 MHz, CDCl3): δ 7.95−7.93 (m,
2H), 7.56−7.52 (m, 1H), 7.47−7.43 (m, 2H), 3.47 (sext, JH,H = 6.72
Hz, 1H), 1.84−1.75 (m, 1H), 1.46−1.38 (m, 1H), 1.31−1.24 (m,
4H), 1.19 (d, JH,H = 6.76 Hz, 3H), 0.86 (t, JH,H = 7.00 Hz, 3H).
13C{1H} NMR (100 MHz, CDCl3): δ 204.7, 136.9, 132.9, 128.7,
JH,H = 7.44 Hz, 1H), 3.65 (sept, JH,H = 6.92 Hz, 1H), 1.56 (d, JH,H
=
7.40 Hz, 3H), 1.26 (d, JH,H = 6.76 Hz, 6H). 13C{1H} NMR (100
6948
J. Org. Chem. 2021, 86, 6943−6951