Domino Alcohol Oxidation/Oxidative Cross-Dehydrogenative Coupling
–
1
3
C
437, 1685, 1666, 1460, 742, 708 cm . HRMS: calcd. for
2-(4-Bromophenyl)-N-(4-cyanophenyl)-2-oxoacetamide (3k): Light
yellow solid; m.p. 190–192 °C. R = 0.43 (20% ethyl acetate in hex-
]DMSO): δ = 11.4 (br. s, 1 H), 8.02–
.07 (m, 2 H), 7.96–8.01 (m, 2 H), 7.84–7.93 (m, 4 H) ppm. 13
+
14
H
10
N
2
O
4
Na [M + Na] 293.0538; found 293.0537.
-Oxo-2-phenyl-N-[4-(trifluoromethyl)phenyl]acetamide (3d): Yellow
solid; m.p. 118–120 °C. R = 0.48 (20% ethyl acetate in hexane).
): δ = 9.14 (br. s, 1 H), 8.41 (dd, J =
.5 Hz, J = 1 Hz, 2 H), 7.84 (d, J = 8.5 Hz, 2 H), 7.61–7.72 (m, 3
H), 7.53 (t, J = 8 Hz, 2 H) ppm. C NMR (125 MHz, CDCl
187.0, 159.1, 139.8, 135.0, 133.0, 131.7, 128.8, 126.6 (q, J =
.63 Hz), 125.2, 123.0, 119.8 ppm. FTIR: ν˜ = 3354, 1668, 1617,
f
1
ane). H NMR (500 MHz, [D
8
6
2
C
f
1
1
6
NMR (125 MHz, [D ]DMSO): δ = 187.6, 162.8, 141.9, 133.8,
H NMR (500 MHz, CDCl
3
2
132.3, 132.1, 131.5, 129.4, 120.5, 118.9, 106.6 ppm. FTIR: ν˜ =
8
–
1
+
13
3426, 3080, 2251, 1657, 1028 cm . MS (EI): m/z = 327.9700 [M] .
3
): δ
=
3
1
N-(4-Cyanophenyl)-2-oxo-2-(3,4,5-trimethoxyphenyl)acetamide (3l):
Yellow solid; m.p. 196–198 °C. R = 0.13 (20% ethyl acetate in hex-
f
–1
1
542, 1334, 1113 cm . HRMS: calcd. for C15
H
11NO
2
F
3
Na [M +
ane). H NMR (500 MHz, [D ]DMSO): δ = 11.37 (br. s, 1 H), 7.99
6
+
Na] 316.0561; found 316.0552.
(d, J = 8.5 Hz, 2 H), 7.91 (d, J = 9 Hz, 2 H), 7.41 (s, 2 H), 3.88 (s,
1
3
6
6
H), 3.84 (s, 3 H) ppm. C NMR (125 MHz, [D ]DMSO): δ =
Ethyl 4-(2-Oxo-2-phenylacetamido)benzoate (3e): Yellow solid; m.p.
1
187.3, 163.3, 153.0, 143.6, 142.0, 133.4, 127.3, 120.4, 118.9, 107.6,
1
(
=
(
07–109 °C. R
500 MHz, CDCl
1 Hz, 2 H), 8.06–8.12 (m, 2 H), 7.76–7.81 (m, 1 H), 7.49–7.55
f
= 0.48 (20% ethyl acetate in hexane). H NMR
1
2
106.4, 60.4, 56.1 ppm. FTIR: ν˜ = 3446, 2998, 2224, 1690, 1658,
3
): δ = 9.13 (br. s, 1 H), 8.42 (dd, J = 8.5 Hz, J
–
1
+
1
177 cm . MS (EI): m/z = 340.0771 [M] .
1
3
m, 1 H), 4.38 (q, J = 7 Hz, 2 H), 1.40 (t, J = 7 Hz, 3 H) ppm.
C
2-(4-Chlorophenyl)-N-(4-cyanophenyl)-2-oxoacetamide (3m): Light
NMR (100 MHz, CDCl
1
3
3
): δ = 187.0, 166.0, 159.0, 140.7, 135.0,
yellow solid; m.p. 226–228 °C. R = 0.46 (20% ethyl acetate in hex-
f
1
33.0, 131.7, 131.1, 128.8, 127.2, 119.3, 61.2, 14.5 ppm. FTIR: ν˜ =
ane). H NMR (500 MHz, [D ]DMSO): δ = 11.4 (br. s, 1 H), 8.14
6
–
1
321, 1704, 1666, 1389, 1279, 858 cm . HRMS: calcd. for
(d, J = 9 Hz, 2 H), 7.99 (d, J = 8 Hz, 2 H), 7.91 (d, J = 9 Hz, 2 H),
[M + H]+ 298.1079; found 298.1084.
13
C
17
H
16NO
4
7.73 (d, J = 8.5 Hz, 2 H) ppm. C NMR (125 MHz, [D ]DMSO):
6
δ = 187.3, 162.7, 141.2, 139.9, 133.4, 131.2, 129.2, 120.4, 118.8,
1
-Phenyl-2-(piperidin-1-yl)ethane-1,2-dione (3f): Yellow solid; m.p.
–
1
1
106.5 ppm. FTIR: ν˜ = 3436, 2223, 1654, 1266 cm . MS (EI): m/z
9
4–96 °C. R
f
= 0.28 (20% ethyl acetate in hexane). H NMR
): δ = 7.91–7.97 (m, 2 H), 7.59–7.66 (m, 1 H),
.50 (t, J = 7.5 Hz, 2 H), 3.67–3.73 (m, 2 H), 3.28 (t, J = 5.5 Hz,
H), 1.65–1.73 (m, 4 H), 1.5–1.58 (m, 2 H) ppm. 13C NMR
): δ = 192.1, 165.6, 134.8, 133.4, 129.7, 129.1,
7.2, 42.3, 26.3, 25.6, 24.5 ppm. FTIR: ν˜ = 2885, 1732, 1637, 1396,
+
=
284.0300 [M] .
-(3-Methylpiperidin-1-yl)-2-phenylethane-1,2-dione (3n): Yellow oil
mixture of cis and trans isomers); R = 0.44 (20% ethyl acetate in
): δ = 7.97–7.92 (m, 4 H),
.67–7.6 (m, 2 H), 7.54–7.47 (m, 4 H), 4.58–4.43 (m, 2 H), 3.38–
.52 (m, 2 H), 3.08–2.96 (m, 1 H), 2.88–2.76 (m, 1 H), 2.74–2.64
(500 MHz, CDCl
3
7
2
1
(
f
(125 MHz, CDCl
3
1
hexane). H NMR (400 MHz, CDCl
7
3
3
4
1
2
–1
H15NO
2
Na [M + Na]+
263, 1047 cm . HRMS: calcd. for C13
40.1000; found 240.1005.
(
m, 1 H), 2.56–2.45 (m, 1 H), 1.92–1.66 (m, 5 H), 1.58–1.40 (m, 2
H), 1.32–1.12 (m, 3 H), 1.06 (d, J = 6.8 Hz, 2 H), 0.80 (d, J =
6.8 Hz, 2 H) ppm. C NMR (100 MHz, CDCl ): δ = 192.0, 165.6,
3
1
f
-Phenyl-2-(pyrrolidin-1-yl)ethane-1,2-dione (3g): Yellow oil; R =
1
3
1
0.41 (30% ethyl acetate in hexane). H NMR (500 MHz, CDCl
3
):
1
2
34.8, 133.5, 129.7, 129.1, 53.5, 48.5, 46.7, 33.1, 33.0, 31.8, 31.2,
δ = 7.93–7.99 (m, 2 H), 7.57–7.63 (m, 1 H), 7.44–7.50 (m, 2 H),
–
1
5.8, 24.9, 19.1, 18.8 ppm. FTIR: ν˜ = 2924, 1600, 1674, 1175 cm .
3
.58–3.65 (m, 2 H), 3.39 (t, J = 6 Hz, 2 H), 1.86–1.97 (m, 4 H) ppm.
+
13
14 18 2
HRMS: calcd. for C H NO [M + H] 232.3025; found 232.3027.
C NMR (125 MHz, CDCl
3
): δ = 191.7, 165.0, 134.7, 133.1, 130.1,
1
1
29.1, 46.8, 45.4, 26.1, 24.2 ppm. FTIR: ν˜ = 2968, 2871, 1672,
1
-(4-Methylpiperidin-1-yl)-2-phenylethane-1,2-dione (3o): Yellow
–1
+
650.7 cm . HRMS: calcd. for C12
H
14NO
2
[M + H] 204.1025;
1
oil; R
CDCl
f
= 0.43 (20% ethyl acetate in hexane). H NMR (400 MHz,
found 204.1028.
3
): δ = 7.96–7.90 (m, 2 H), 7.66–7.6 (m, 1 H), 7.5 (t, J = 7 Hz,
1
1
(
7
-Morpholino-2-phenylethane-1,2-dione (3h): Yellow oil; R
f
= 0.35
30% ethyl acetate in hexane). H NMR (500 MHz, CDCl ): δ =
.93 (d, J = 8 Hz, 2 H), 7.63 (td, J = 7 Hz, J = 0.5 Hz, 1 H), 7.49
3 H), 4.67–4.58 (m, 1 H), 3.56–3.48 (m, 1 H), 3.05 (td, J = 12.5 Hz,
1
2
J = 3 Hz, 1 H), 2.79 (td,
(m, 4 H), 1.08–1.30 (m, 3 H), 0.97 (d, J = 6.5 Hz, 3 H) ppm. 13
C
1
J = 12.5 Hz, J = 3 Hz, 1 H), 1.83–1.57
2
3
1
2
(
(
1
t, J = 7.5 Hz, 2 H), 3.76 (s, 4 H), 3.62 (t, J = 4.5 Hz, 2 H), 3.55
NMR (100 MHz, CDCl ): δ = 192.0, 165.6, 134.8, 133.5, 129.7,
129.1, 46.5, 41.7, 34.4, 33.7, 31.2, 21.7 ppm. FTIR: ν = 2924, 1741,
3
13
t, J = 4.5 Hz, 2 H) ppm. C NMR (125 MHz, CDCl
65.5, 135.0, 133.1, 129.7, 129.0, 66.8, 66.7, 46.3, 41.7 ppm. FTIR: 1639, 1122 cm . HRMS: calcd. for C14
232.3035; found 232.3036.
3
): δ = 191.2,
˜
–
1
+
2
H18NO [M + H]
–1
ν˜ = 3437, 2863, 1732, 1666, 1637, 1448, 1107 cm . HRMS: calcd.
for C12
+
3
H13NO [M + H] 220.0974; found 220.0975.
N-[4-(Benzyloxy)phenyl]-2-oxo-2-[4-(trifluoromethyl)phenyl] Acet-
amide (6): Pale yellow solid; m.p. 120–122 °C. R = 0.44 (10% ethyl
): δ = 8.87 (br. s, 1
H), 8.53 (dd, J = 8.75 Hz, J = 1 Hz, 2 H), 7.77 (d, J = 8 Hz, 2
N-(4-Cyanophenyl)-2-oxo-2-(4-trifluoromethyl)phenylacetamide (3i):
Light yellow solid; m.p. 190–192 °C. R
in hexane). H NMR (400 MHz, [D
f
1
= 0.43 (20% ethyl acetate acetate in hexane). H NMR (500 MHz, CDCl
3
f
1
1
2
6
]DMSO): δ = 11.43 (br. s, 1
H), 8.32 (d, J = 8 Hz, 2 H), 7.98–8.05 (m, 4 H), 7.89–7.94 (m, 2 H), 7.59–7.65 (m, 2 H), 7.42–7.47 (m, 2 H), 7.36–7.42 (m, 2 H),
H) ppm. 13C NMR (100 MHz, [D
]DMSO): δ = 187.4, 162.1, 7.31–7.35 (m, 1 H), 6.98–7.04 (m, 2 H), 5.08 (s, 2 H) ppm. 13
41.8, 135.9, 133.4, 131.3, 125.9 (q, J = 3.63 Hz), 125.0, 122.3,
NMR (125 MHz, CDCl ): δ = 186.9, 158.0, 156.6, 136.9, 136.0,
20.5, 118.9, 106.6 ppm. FTIR: ν˜ = 3439, 2250, 1657, 1561, 135.7, 135.5, 132.0, 129.9, 128.8, 128.2, 127.6, 125.6 (q, J =
C
6
1
1
1
3
–
1
+
173 cm . MS (EI): m/z = 318.0500 [M] .
3.63 Hz), 121.7, 115.6, 70.4 ppm. FTIR: ν˜ = 3454, 3022, 1685,
668, 1215 cm . HRMS: calcd. for C12
38.0719; found 438.0718.
–
1
+
1
4
3 3
H16NO KF [M + K]
N-(4-Cyanophenyl)-2-(2,4-dichlorophenyl)-2-oxoacetamide
White solid; m.p. 172–174 °C. R = 0.40 (20% ethyl acetate in hex-
]DMSO): δ = 11.47 (br. s, 1 H), 7.99
d, J = 8.8 Hz, 2 H), 7.88–7.93 (m, 3 H), 7.87 (d, J = 2 Hz, 2 H), Intermediate: An oven-dried Schlenk tube was charged with
(3j):
f
1
ane). H NMR (400 MHz, [D
6
Experimental Procedure for the Synthesis of Derivative of Reaction
(
1
2
13
7
.68 (dd, J = 8.4 Hz, J = 2 Hz, 1 H) ppm. C NMR (100 MHz,
]DMSO): δ = 188.3, 161.3, 141.9, 138.3, 133.5, 133.3, 133.2,
32.3, 130.0, 127.9, 120.5, 118.8, 106.7 ppm. FTIR: ν˜ = 3429, 3014,
Fe(OAc)
2
(8.6 mg,
0.05 mmol),
2,2Ј-bipyridine
(7.8 mg,
[D
6
0.05 mmol), pyridine (40 μL, 0.5 mmol), 2-hydroxyacetophenone
(34.5 mg, 0.25 mmol), 4-nitroaniline (35.8 mg, 0.3 mmol), TEMPO
(11.5 mg, 0.015 mmol), ethyl iodide(20 μL, 0.25 mmol), and a mag-
1
2
–1
+
251, 1733, 1657, 1046 cm . MS (EI): m/z = 318.5477 [M] .
Eur. J. Org. Chem. 2014, 7451–7457
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7455