The Journal of Organic Chemistry
Article
carbamate (0.20 mmol), p-tolylboronic acid (2.0 equiv), K CO (3.0
equiv), and PEPPSI-IPr (3 mol %) in THF (0.25 M) for 15 h at 60 °C
and chromatography, the title compound in 95% yield (41.5 mg).
2
3
1
White solid. H NMR (500 MHz, CDCl ) δ 7.76 (d, J = 7.6 Hz, 2H),
3
afforded, after filtration and chromatography, the title compound in
7.68 (t, J = 9.1 Hz, 1H), 7.63−7.58 (m, 2H), 7.50 (t, J = 7.6 Hz, 2H),
1
13
9
2% yield (36.2 mg). White solid. H NMR (500 MHz, CDCl ) δ 7.78
7.30−7.24 (m, 1H). C NMR (125 MHz, CDCl ) δ 194.1, 153.3 (J =
3
3
(
7
d, J = 7.5 Hz, 2H), 7.72 (d, J = 7.4 Hz, 2H), 7.57 (t, J = 7.3 Hz, 1H),
.47 (t, J = 7.4 Hz, 2H), 7.28 (d, J = 7.6 Hz, 2H), 2.44 (s, 3H). 13
NMR (125 MHz, CDCl ) δ 196.5, 143.3, 138.0, 134.9, 132.2, 130.3,
256.3 Hz, J = 12.9 Hz), 150.2 (J = 251.1 Hz, J = 13.2 Hz), 136.9, 134.5
(J = 4.1 Hz), 132.8, 129.9, 128.5, 127.1 (J = 7.2 Hz, J = 3.7 Hz), 119.3
(J = 18.1 Hz, J = 1.3 Hz), 117.3 (J = 17.8 Hz). 19F NMR (471 MHz,
C
3
1
30.0, 129.0, 128.2, 21.7. Spectroscopic data matched literature
CDCl ) δ −130.6, −136.2. Spectroscopic data matched literature
3
6d
4
values.
values.
(
4-Methoxyphenyl)(phenyl)methanone (3d) (Table 2, Entry
4-Benzoylbenzonitrile (3i) (Table 3, Amide = N-Glutarimide).
According to the general procedure, the reaction of 1-(4-cyano-
benzoyl)piperidine-2,6-dione (0.20 mmol), phenylboronic acid (2.0
equiv), K CO (3.0 equiv), and PEPPSI-IPr (3 mol %) in THF (0.25
1
4). According to the general procedure, the reaction of tert-butyl
benzoyl(phenyl)carbamate (0.20 mmol), (4-methoxyphenyl)boronic
acid (2.0 equiv), K CO (3.0 equiv), and PEPPSI-IPr (3 mol %) in
THF (0.25 M) for 15 h at 60 °C afforded, after filtration and
chromatography, the title compound in 98% yield (41.6 mg). White
solid. H NMR (500 MHz, CDCl ) δ 7.83 (d, J = 8.4 Hz, 2H), 7.76 (d,
2
3
2
3
M) for 15 h at 60 °C afforded, after filtration and chromatography, the
1
title compound in 82% yield (34.0 mg). White solid. H NMR (500
1
3
MHz, CDCl ) δ 7.88 (d, J = 7.6 Hz, 2H), 7.82−7.74 (m, 4H), 7.64 (t,
3
13
J = 7.5 Hz, 2H), 7.56 (t, J = 7.3 Hz, 1H), 7.47 (t, J = 7.3 Hz, 2H), 6.97
J = 7.2 Hz, 1H), 7.52 (t, J = 7.3 Hz, 2H). C NMR (125 MHz,
(
1
d, J = 8.4 Hz, 2H), 3.89 (s, 3H). 13C NMR (125 MHz, CDCl ) δ
CDCl ) δ 195.1, 141.3, 136.4, 133.4, 132.2, 130.3, 130.1, 128.7, 118.0,
3
3
6
d
95.6, 163.2, 138.3, 132.6, 131.9, 130.2, 129.8, 128.2, 113.6, 55.5.
Spectroscopic data matched literature values.
Methyl 4-Benzoylbenzoate (3e) (Table 2, Entry 15). According
to the general procedure, the reaction of tert-butyl benzoyl(phenyl)-
carbamate (0.20 mmol), (4-(methoxycarbonyl)phenyl)boronic acid
2.0 equiv), K CO (3.0 equiv), and PEPPSI-IPr (3 mol %) for 15 h at
0 °C afforded, after filtration and chromatography, the title
compound in 90% yield (43.2 mg). White solid. H NMR (500
MHz, CDCl ) δ 8.15 (d, J = 8.1 Hz, 2H), 7.84 (d, J = 8.1 Hz, 2H),
115.7. Spectroscopic data matched literature values.
6d
Phenyl(4-(trifluoromethyl)phenyl)methanone (3j) (Table 3,
Amide = N-Glutarimide). According to the general procedure, the
reaction of 1-(4-(trifluoromethyl)benzoyl)piperidine-2,6-dione (0.20
mmol), phenylboronic acid (2.0 equiv), K CO (3.0 equiv), and
2 3
(
6
PEPPSI-IPr (3 mol %) in THF (0.25 M) for 15 h at 60 °C afforded,
2
3
after filtration and chromatography, the title compound in 98% yield
1
1
(49.2 mg). White solid. H NMR (500 MHz, CDCl
) δ 7.90 (d, J =
3
7.7 Hz, 2H), 7.81 (d, J = 7.3 Hz, 2H), 7.76 (d, J = 7.6 Hz, 2H), 7.63 (t,
3
J = 7.3 Hz, 1H), 7.51 (t, J = 7.2 Hz, 2H). 13C NMR (125 MHz,
7
2
1
.80 (d, J = 7.7 Hz, 2H), 7.62 (t, J = 7.3 Hz, 1H), 7.50 (t, J = 7.6 Hz,
H), 3.97 (s, 3H). 13C NMR (125 MHz, CDCl ) δ 196.0, 166.3,
CDCl
4.2 Hz), 128.6, 125.4 (J = 3.6 Hz), 123.7 (J = 258.1 Hz). F NMR
(471 MHz, CDCl ) δ −63.0. Spectroscopic data matched literature
) δ 195.6, 140.8, 136.8, 133.7 (J = 32.5 Hz), 133.1, 130.1 (J =
3
3
1
9
41.3, 137.0, 133.2, 133.0, 130.1, 129.8, 129.5, 128.5, 52.5.
Spectroscopic data matched literature values.
Cross-Coupling of Amides: Variation of Amides. Methyl 4-
Benzoylbenzoate (3e) (Table 3, Amide = N-Glutarimide).
According to the general procedure, the reaction of 1-(4-(methoxy-
carbonyl)benzoyl)piperidine-2,6-dione (0.20 mmol), phenylboronic
acid (2.0 equiv), K CO (3.0 equiv), and PEPPSI-IPr (3 mol %) in
THF (0.25 M) for 15 h at 60 °C afforded, after filtration and
chromatography, the title compound in 93% yield (44.7 mg). White
solid. H NMR (500 MHz, CDCl ) δ 8.15 (d, J = 8.1 Hz, 2H), 7.84 (d,
6d
3
6
d
values.
Benzo[d][1,3]dioxol-5-yl(phenyl)methanone (3k) (Table 3,
Amide = N-Glutarimide). According to the general procedure, the
reaction of 1-(benzo[d][1,3]dioxole-5-carbonyl)piperidine-2,6-dione
(0.20 mmol), phenylboronic acid (2.0 equiv), K CO (3.0 equiv), and
2
3
2 3
PEPPSI-IPr (3 mol %) in THF (0.25 M) for 15 h at 60 °C afforded,
after filtration and chromatography, the title compound in 90% yield
1
1
(40.7 mg). White solid. H NMR (500 MHz, CDCl
) δ 7.74 (d, J =
3
3
J = 8.1 Hz, 2H), 7.80 (d, J = 7.7 Hz, 2H), 7.62 (t, J = 7.3 Hz, 1H), 7.50
7.4 Hz, 2H), 7.56 (t, J = 7.3 Hz, 1H), 7.47 (t, J = 7.3 Hz, 2H), 7.38 (d,
13
(
1
5
t, J = 7.6 Hz, 2H), 3.97 (s, 3H). 13C NMR (125 MHz, CDCl ) δ
J = 9.0 Hz, 2H), 6.86 (d, J = 7.8 Hz, 1H), 6.07 (s, 2H). C NMR (125
3
96.0, 166.3, 141.3, 137.0, 133.2, 133.0, 130.1, 129.8, 129.5, 128.5,
MHz, CDCl ) δ 195.2, 151.5, 148.0, 138.1, 132.0, 131.9, 129.7, 128.2,
3
6d
2.5. Spectroscopic data matched literature values.
3-Methoxyphenyl)(phenyl)methanone (3f) (Table 3, Amide
N-Glutarimide). According to the general procedure, the reaction
126.9, 109.9, 107.7, 101.9. Spectroscopic data matched literature
4
(
values.
=
Phenyl(o-tolyl)methanone (3b) (Table 3, Amide = N-Ts/Ph).
According to the general procedure, the reaction of methyl 2-methyl-
N-phenyl-N-tosylbenzamide (0.20 mmol), phenylboronic acid (2.0
of 1-(3-methoxybenzoyl)piperidine-2,6-dione (0.20 mmol), phenyl-
boronic acid (2.0 equiv), K CO (3.0 equiv), and PEPPSI-IPr (3 mol
2
3
%
) in THF (0.25 M) for 15 h at 60 °C afforded, after filtration and
equiv), K CO (3.0 equiv), and PEPPSI-IPr (3 mol %) in THF (0.25
2 3
chromatography, the title compound in 96% yield (40.8 mg). White
solid. H NMR (500 MHz, CDCl ) δ 7.81 (d, J = 7.7 Hz, 2H), 7.59 (t,
M) for 15 h at 110 °C afforded, after filtration and chromatography,
1
1
the title compound in 91% yield (35.7 mg). Oil. H NMR (500 MHz,
3
J = 7.3 Hz, 1H), 7.48 (t, J = 7.5 Hz, 2H), 7.40−7.33 (m, 3H), 7.14 (d,
CDCl
3
) δ 7.83 (d, J = 7.6 Hz, 2H), 7.61 (t, J = 7.3 Hz, 1H), 7.48 (t, J =
J = 7.1 Hz, 1H), 3.86 (s, 3H). 13C NMR (125 MHz, CDCl ) δ 196.5,
7.4 Hz, 2H), 7.42 (t, J = 7.4 Hz, 1H), 7.33 (t, J = 9.4 Hz, 2H), 7.28 (d,
J = 5.9 Hz, 1H), 2.36 (s, 3H). C NMR (125 MHz, CDCl
138.6, 137.8, 136.8, 133.2, 131.0, 130.3, 130.2, 128.5, 128.5, 125.2,
20.0. Spectroscopic data matched literature values.
(2-Fluorophenyl)(phenyl)methanone (3l) (Table 3, Amide =
N-Ts/Ph). According to the general procedure, the reaction of 2-
fluoro-N-phenyl-N-tosylbenzamide (0.20 mmol), phenylboronic acid
3
13
1
59.6, 138.9, 137.7, 132.4, 130.1, 129.2, 128.3, 122.9, 118.9, 114.3,
) δ 198.7,
3
6d
5
5.5. Spectroscopic data matched literature values.
Phenyl(m-tolyl)methanone (3g) (Table 3, Amide = N-
Glutarimide). According to the general procedure, the reaction of
-(3-methylbenzoyl)piperidine-2,6-dione (0.20 mmol), phenylboronic
acid (2.0 equiv), K CO (3.0 equiv), and PEPPSI-IPr (3 mol %) in
6
d
1
2
3
THF (0.25 M) for 15 h at 60 °C afforded, after filtration and
chromatography, the title compound in 98% yield (38.3 mg). Oil. H
(2.0 equiv), K CO (3.0 equiv), and PEPPSI-IPr (3 mol %) in THF
2 3
1
(0.25 M) for 15 h at 110 °C afforded, after filtration and
NMR (500 MHz, CDCl ) δ 7.81−7.79 (m, 2H), 7.63 (s, 1H), 7.61−
chromatography, the title compound in 98% yield (39.2 mg). Oil.
3
1
7
.57 (m, 2H), 7.48 (t, J = 7.7 Hz, 2H), 7.41−7.57.34 (m, 2H), 2.43 (s,
H NMR (500 MHz, CDCl ) δ 7.85 (d, J = 7.5 Hz, 2H), 7.61 (t, J =
3
13
3H). C NMR (125 MHz, CDCl ) δ 197.0, 138.2, 137.8, 137.7, 133.2,
7.3 Hz, 1H), 7.57−7.51 (m, 2H), 7.48 (t, J = 7.4 Hz, 2H), 7.28 (d, J =
3
7.4 Hz, 1H), 7.17 (t, J = 9.0 Hz, 1H). 13C NMR (125 MHz, CDCl ) δ
1
32.3, 130.5, 130.1, 128.3, 128.1, 127.4, 21.4. Spectroscopic data
3
6b
matched literature values.
193.5, 160.1 (J = 252.4 Hz), 137.4, 133.4, 133.1 (J = 8.3 Hz), 130.8 (J
= 2.8 Hz), 129.8, 128.5, 127.1 (J = 14.7 Hz), 124.3 (J = 3.6 Hz), 116.3
(
3,4-Difluorophenyl)(phenyl)methanone (3h) (Table 3,
(J = 21.8 Hz). 19F NMR (471 MHz, CDCl ) δ −111.0. Spectroscopic
Amide = N-Glutarimide). According to the general procedure, the
reaction of 1-(3,4-difluorobenzoyl)piperidine-2,6-dione (0.20 mmol),
phenylboronic acid (2.0 equiv), K CO (3.0 equiv), and PEPPSI-IPr
3
6
d
data matched literature values.
2
3
Phenyl(thiophen-2-yl)methanone (3m) (Table 3, Amide = N-
Ts/Ph). According to the general procedure, the reaction of N-phenyl-
(
3 mol %) in THF (0.25 M) for 15 h at 60 °C afforded, after filtration
G
J. Org. Chem. XXXX, XXX, XXX−XXX