Pd-Catalyzed ortho-C–H Acylation under Aqueous Conditions
{2-[1-(Methoxyimino)ethyl]phenyl}(m-tolyl)methanone (3i):[5b] Pale
[4-(tert-Butyl)phenyl][2-(pyridin-2-yl)phenyl]methanone (5g): White
yellow solid, yield 80%. 1H NMR (CDCl3, 400 MHz): δ = 7.55– solid, yield 75%. 1H NMR (CDCl3, 400 MHz): δ = 8.40 (d, J =
7.47 (m, 6 H), 7.34–7.26 (m, 2 H), 3.70 (s, 3 H), 2.37 (s, 3 H), 2.02
(s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = δ = 197.6, 154.1,
138.9, 138.1, 137.9, 136.5, 133.2, 130.1, 129.7, 128.9, 128.4, 128.0,
127.6, 126.6, 61.5, 21.2, 14.4 ppm. MS (EI): m/z (%) = 267, 236,
222, 176, 91.
4.36 Hz, 1 H), 7.76 (d, J = 7.68 Hz, 1 H), 7.65–7.46 (m, 7 H), 7.30
(d, J = 8.4 Hz, 2 H), 7.02 (t, J = 5.98 Hz, 1 H), 1.27 (s, 9 H) ppm.
13C NMR (CDCl3, 100 MHz): δ = 197.8, 157.0, 156.0, 149.1, 139.7,
139.6, 136.1, 135.1, 130.0, 129.6, 128.9, 128.89, 128.2, 124.9, 122.8,
121.7, 34.9, 31.0 ppm. MS (EI): m/z (%) = 315, 286, 182, 127, 77.
HRMS calcd. for: C22H22NO [M + H]+ 316.1695; found 316.1694.
{2-[1-(Methoxyimino)ethyl]phenyl}(naphthalen-2-yl)methanone (3j):
1
(2-Chlorophenyl)[2-(pyridin-2-yl)phenyl]methanone (5h):[12] CAS
Yellow solid, yield 77%. H NMR (CDCl3, 400 MHz): δ = 8.08 (s,
1
1 H), 7.96–7.82 (m, 4 H), 7.59–7.50 (m, 6 H), 3.63 (s, 3 H), 2.02 (s,
3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 197.4, 154.0, 138.9,
136.5, 135.5, 135.3, 132.3, 131.0, 130.1, 129.3, 129.0, 128.5, 128.14,
128.12, 127.7, 127.68, 126.5, 124.9, 61.5, 14.3 ppm. MS (EI): m/z
(%) = 303, 272, 202, 127, 77. HRMS calcd. for: C20H18NO2 [M +
H]+ 304.1332; found 304.1332.
Phenyl[2-(pyridin-2-yl)phenyl]methanone (5a):[12] CAS number
198478-48-7. White solid, yield 78%. 1H NMR (CDCl3, 400 MHz):
δ = 8.50 (d, J = 4.36 Hz, 1 H), 7.71–7.54 (m, 5 H), 7.45–7.43 (m,
1 H), 7.28–7.15 (m, 4 H), 7.06–7.01 (m, 2 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 198.1, 156.7, 148.9, 139.5, 137.9, 136.2,
132.2, 130.1, 129.4, 129.0, 128.7, 128.4, 127.9, 122.6, 121.8 ppm.
MS (EI): m/z (%) = 259, 230, 182, 127, 77.
[2-(Pyridin-2-yl)phenyl](p-tolyl)methanone (5b):[12] CAS number
1173294-90-0. White solid, yield 75 %. 1H NMR (CDCl3,
400 MHz): δ = 8.39 (d, J = 4.30 Hz, 1 H), 7.77 (d, J = 7.64 Hz, 1
H), 7.62–7.47 (m, 7 H), 7.09–7.01 (m, 3 H), 2.32 (s, 3 H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 197.9, 156.9, 149.0, 143.1, 139.6,
139.5, 136.2, 135.2, 130.0, 129.7, 128.9, 128.8, 128.7, 128.3, 122.8,
121.8, 21.5 ppm. MS (EI): m/z (%) = 273, 244, 182, 127, 91.
number 1271322-37-2. White solid, yield 78%. H NMR (CDCl3,
400 MHz): δ = 8.36 (d, J = 4.12 Hz, 1 H), 7.77 (d, J = 7.68 Hz, 1
H), 7.70–7.48 (m, 8 H), 7.40–7.36 (m, 1 H), 7.01 (t, J = 6.0 Hz, 1
H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 196.1, 157.2, 149.0,
140.5, 139.3, 138.1, 136.1, 132.9, 131.5, 131.1, 130.5, 130.2, 129.3,
128.5, 125.9, 122.8, 121.8 ppm. MS (EI): m/z (%) = 293, 258, 230,
182, 127.
[2-(Pyridin-2-yl)phenyl](m-tolyl)methanone (5i):[12] CAS number
1271322-40-7. White solid, yield 67 %. 1H NMR (CDCl3,
400 MHz): δ = 8.38 (d, J = 4.36 Hz, 1 H), 7.76 (d, J = 7.64 Hz, 1
H), 7.62–7.46 (m, 7 H), 7.22–7.13 (m, 2 H), 7.04–7.01 (m, 1 H),
2.28 (s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 198.3, 156.9,
149.0, 139.7, 139.6, 137.73, 137.70, 136.2, 133.1, 130.1,129.9, 129.1,
128.8, 128.3, 127.9, 126.9, 122.7, 121.9, 21.1 ppm. MS (EI): m/z
(%) = 273, 244, 182, 127, 91.
(E)-Phenyl[2-(phenyldiazenyl)phenyl]methanone (7a):[10c] CAS
number 54184-68-8. Red solid, yield 73 %. 1H NMR (CDCl3,
400 MHz): δ = 7.95 (d, J = 7.56 Hz, 1 H), 7.77 (d, J = 7.12 Hz, 2
H), 7.66–7.60 (m, 3 H), 7.48–7.33 (m, 8 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 197.1, 152.1, 150.4, 138.5, 136.9, 132.7,
131.3, 130.8, 130.7, 129.4, 128.9, 128.8, 128.3, 122.9, 120.0 ppm.
MS (EI): m/z (%) = 286, 270, 152, 105, 77.
(4-Methoxyphenyl)[2-(pyridin-2-yl)phenyl]methanone (5c):[12] CAS
1
number 1236046-45-9. White solid, yield 72%. H NMR (CDCl3,
400 MHz): δ = 8.42 (d, J = 4.28 Hz, 1 H), 7.77 (d, J = 7.68 Hz, 1
H), 7.68 (d, J = 8.64 Hz, 2 H), 7.61–7.45 (m, 5 H), 7.06–7.03 (m,
1 H), 6.76 (d, J = 8.72 Hz, 2 H), 3.79 (s, 3 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 196.9, 162.9, 156.9, 149.1, 139.6, 139.4,
136.1, 131.8, 130.7, 130.0, 128.9, 128.7, 128.3, 122.9, 121.8, 113.3,
55.3 ppm. MS (EI): m/z (%) = 289, 260, 182, 127, 77.
(E)-[2-(Phenyldiazenyl)phenyl](p-tolyl)methanone (7b):[10c] Red so-
lid, yield 61 %. 1H NMR (CDCl3, 400 MHz): δ = 7.94 (d, J =
7.08 Hz, 1 H), 7.69–7.56 (m, 5 H), 7.47 (s, 2 H), 7.36 (s, 3 H),
7.18 (d, J = 6.60 Hz, 2 H), 2.36 (s, 3 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 196.7, 152.1, 150.3, 143.6, 137.4, 135.9, 131.2, 130.8,
130.5, 129.6, 129.1, 128.9, 128.6, 122.9, 119.7, 21.61 ppm. MS (EI):
m/z (%) = 300, 284, 165, 152, 77.
(4-Fluorophenyl)[2-(pyridin-2-yl)phenyl]methanone (5d):[12] CAS
1
number 1236046-46-0. White solid, yield 80%. H NMR (CDCl3,
(E)-(4-Methoxyphenyl)[2-(phenyldiazenyl)phenyl]methanone (7c):[10c]
400 MHz): δ = 8.36 (d, J = 4.12 Hz, 1 H), 7.78–7.51 (m, 8 H), 7.07–
7.00 (m, 1 H), 6.93 (t, J = 8.52 Hz, 2 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 196.6, 165.2 (d, J = 252.5 Hz), 156.5, 148.9, 139.3,
139.1, 136.4, 134.2 (d, J = 2.62 Hz), 131.9 (d, J = 9.23 Hz), 130.2,
128.9, 128.7, 128.5, 122.6, 122.0, 115.1 (d, J = 21.76 Hz) ppm. MS
(EI): m/z (%) = 277, 248, 182, 127, 95.
1
Red solid, yield 62%. H NMR (CDCl3, 400 MHz): δ = 7.93 (d, J
= 7.04 Hz, 1 H), 7.77 (d, J = 7.52 Hz, 2 H), 7.63–7.51 (m, 5 H),
7.37 (s, 3 H), 6.86 (d, J = 7.60 Hz, 2 H), 3.82 (s, 3 H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 195.7, 163.4, 152.2, 150.1, 137.8,
131.9, 131.4, 131.3, 130.8, 130.4, 128.9, 128.5, 123.0, 119.3, 113.6,
55.4 ppm. MS (EI): m/z (%) = 316, 300, 168, 135, 77.
(4-Chlorophenyl)[2-(pyridin-2-yl)phenyl]methanone (5e):[12] CAS
(E)-(4-Fluorophenyl)[2-(phenyldiazenyl)phenyl]methanone (7d):[10c]
CAS number 1421276-20-1. Red solid, yield 71 %. 1H NMR
(CDCl3, 400 MHz): δ = 7.96 (d, J = 7.20 Hz, 1 H), 7.80 (s, 2 H),
7.67–7.57 (m, 3 H), 7.47 (s, 2 H) 7.37 (s, 3 H), 7.04 (d, J = 7.4 Hz,
2 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 195.5, 166.7, 164.2,
151.9, 150.3, 136.5, 134.8, 131.9 (d, J = 9.25 Hz), 131.5, 130.9 (d,
J = 3.13 Hz), 129.4, 128.9, 128.6, 122.8, 120.2, 115.4 (d, J =
21.87 Hz) ppm. MS (EI): m/z (%) = 304, 199, 170, 95, 77.
1
number 1173294-91-1. White solid, yield 73%. H NMR (CDCl3,
400 MHz): δ = 8.34 (d, J = 4.2 Hz, 1 H), 7.77 (d, J = 7.68 Hz, 1
H), 7.63–7.52 (m, 7 H), 7.23 (d, J = 8.4 Hz, 2 H), 7.04 (t, J =
5.92 Hz, 1 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 196.7, 156.4,
148.8, 139.3, 139.0, 138.4, 136.4, 130.6, 130.2, 128.9, 128.58,
128.55, 128.54, 128.2, 122.4, 122.0 ppm. MS (EI): m/z (%) = 293,
264, 182, 127, 111.
(4-Bromophenyl)[2-(pyridin-2-yl)phenyl]methanone (5f):[12] CAS
number 1173294-92-2. Pale yellow solid, yield 70 %. 1H NMR
(CDCl3, 400 MHz): δ = 8.34 (d, J = 4.24 Hz, 1 H), 7.77 (d, J =
7.72 Hz, 1 H), 7.62–7.52 (m, 7 H), 7.40 (d, J = 8.4 Hz, 2 H), 7.05
(t, J = 5.88 Hz, 1 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 196.9,
156.3, 148.8, 139.3, 138.9, 136.8, 136.4, 131.2, 130.7, 130.3, 128.9,
128.58, 128.56, 127.2, 122.4, 122.1 ppm. MS (EI): m/z (%) = 337,
308, 182, 127, 76.
(E)-(4-Chlorophenyl)[2-(phenyldiazenyl)phenyl]methanone (7e):[10c]
CAS number 1421276-19-8. Red solid, yield 73 %. 1H NMR
(CDCl3, 400 MHz): δ = 7.97 (d, J = 7.20 Hz, 1 H), 7.72–7.57 (m,
5 H), 7.46–7.34 (m, 7 H) ppm. 13C NMR (CDCl3, 100 MHz): δ =
195.8, 151.9, 150.3, 139.1, 136.9, 136.2, 131.5, 131.0, 130.9, 130.7,
129.0, 128.7, 128.6, 122.9, 120.5 ppm. MS (EI): m/z (%) = 320, 152,
139, 105, 77.
Eur. J. Org. Chem. 2015, 7919–7925
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7923