4
X. Li et al. / Tetrahedron xxx (2015) 1e5
a Bruker micrOTOF-Q II analyzer. 200e300 mesh silica gel was used
for column chromatography.
HRMS m/z (ESI) calcd for C13H10BrO (MþH)þ 260.9909, found
260.9913.
4.2. General procedure for synthesis of bisaryl ketones 2
4.2.7. (3,4-Dimethylphenyl)(phenyl)methanone (2g).31 White solid;
yield: 70%; mp 45.7e46.5 ꢀC; 1H NMR (400 MHz, CDCl3)
d: 7.79 (t,
An oven-dried Schlenk tube was charged with a magnetic stir-
bar, 1,2-diarylalkynes 1 (0.5 mmol), aniline (0.6 mmol), K2CO3
(0.5 mmol), Cu(OAc)2 (0.075 mmol), DMSO (3 mL), The tube was
sealed, and oxygen was purged through syringe. Reaction was
stirred at 120 ꢀC for 16e18 h. After the reaction was finished, the
reaction mixture was diluted in 30 mL ethyl acetate, filtered on
Celite pad. The organic portion was washed with a saturated
solution of brine (8 mL), saturated NH4Cl (8 mL), a saturated
solution of brine (8 mL), dried (Na2SO4) and concentrated in
vacuum, and the resulting residue was purified by silica gel col-
umn chromatography (hexane/ethyl acetate) to afford the desired
products 2.
J¼4.2 Hz, 2H), 7.61 (s, 1H), 7.59e7.52 (m, 2H), 7.49 (t, J¼7.6 Hz, 2H),
7.23 (d, J¼7.6 Hz, 1H), 2.35 (s, 3H), 2.32 (s, 3H); 13C NMR (100 MHz,
CDCl3) d: 198.3, 141.9, 138.0, 136.7, 135.3, 132.0, 131.1, 129.9, 129.4,
128.1, 128.0, 20.0, 19.7; IR (neat cmꢁ1): 1661 (C]O); LRMS (EI
70 eV) m/z (%): 210 (Mþ, 100); HRMS m/z (ESI) calcd for C15H15
(MþH)þ 211.1116, found 211.1111.
O
4.2.8. Phenyl(m-tolyl)methanone (2h).32 Yellowish oil; yield: 61%;
1H NMR (400 MHz, CDCl3)
: 7.81 (dd, J¼1.2 Hz, J¼8.4 Hz, 2H),
7.62e7.57 (m, 3H), 7.46e7.40 (m, 2H), 7.38 (dd, J¼4.4 Hz, J¼4.4 Hz,
2H), 2.41 (s, 3H); 13C NMR (100 MHz, CDCl3)
: 196.8, 138.1, 137.4,
d
d
137.1, 133.0, 132.1, 130.6, 130.1, 128.4, 128.0, 127.2, 21.3; IR (neat
cmꢁ1): 1663 (C]O); LRMS (EI 70 eV) m/z (%): 196 (Mþ, 100); HRMS
m/z (ESI) calcd for C14H13O (MþH)þ 197.0960, found 197.0954.
4.2.1. Benzophenone (2a).17 White solid; yield: 72%; mp
48.0e48.5 ꢀC; 1H NMR (400 MHz, CDCl3)
d
: 7.83 (dd, J¼8.0 Hz,
J¼1.6 Hz, 4H), 7.61e7,56 (m, 2H), 7.51e7.45 (m, 4H); 13C NMR
4.2.9. (3-Chlorophenyl)(phenyl)methanone (2i).17 White solid;
(100 MHz, CDCl3)
d
: 196.7, 137.8, 132.5, 130.2, 128.4; IR (neat cmꢁ1):
yield: 55%; mp 83.8e84.6 ꢀC; 1H NMR (400 MHz, CDCl3)
d:
1660 (C]O); LRMS (EI 70 eV) m/z (%): 182 (Mþ, 100); HRMS m/z
(ESI) calcd for C13H11O (MþH)þ 183.0804, found 183.0801.
7.80e7.71 (m, 3H), 7.68e7.65 (m, 1H), 7.63e7.59 (m, 1H), 7.56e7.54
(m, 1H), 7.51 (dd, J¼4.8 Hz, J¼4.0 Hz, 2H), 7.43 (dd, J¼6.0 Hz,
J¼6.4 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d: 195.5, 139.4, 137.0,
4.2.2. Phenyl(p-tolyl)methanone (2b).17 White solid; yield: 63%; mp
135.2, 133.0, 132.6, 130.2, 130.0, 129.6, 128.4, 128.1; IR (neat cmꢁ1):
1657 (C]O); LRMS (EI 70 eV) m/z (%): 218 (36), 216 (Mþ, 90); HRMS
m/z (ESI) calcd for C13H10ClO (MþH)þ 217.0415, found 217.0421.
56.2e57.0 ꢀC; 1H NMR (400 MHz, CDCl3)
d
: 7.79 (d, J¼7.2 Hz, 2H),
7.73 (d, J¼8.0 Hz, 2H), 7.59 (t, J¼7.4 Hz, 1H), 7.48 (t, J¼7.6 Hz, 2H),
7.28 (d, J¼8.0 Hz, 2H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3)
d:
196.4, 143.2, 137.9, 134.8, 132.1, 130.2, 129.8, 128.9, 128.1, 21.6; IR
(neat cmꢁ1): 1658 (C]O); LRMS (EI 70 eV) m/z (%): 196 (Mþ, 100);
HRMS m/z (ESI) calcd for C14H13O (MþH)þ 197.0960, found
197.0963.
4.2.10. Phenyl(o-tolyl)methanone (2j).17 Yellowish oil; yield: 69%;
1H NMR (400 MHz, CDCl3)
d
: 7.74 (d, J¼7.2 Hz, 2H), 7.54e7.50 (m,
1H), 7.43e7.36 (m, 2H), 7.33e7.26 (m, 1H), 7.25e7.20 (m, 3H); 2.33
(s, 3H); 13C NMR (100 MHz, CDCl3)
d: 198.5,138.8,138.1, 137.0,133.5,
131.7, 130.6, 130.3, 129.0, 128.8, 125.4, 20.4; IR (neat cmꢁ1): 1647
(C]O); LRMS (EI 70 eV) m/z (%): 196 (Mþ, 100); HRMS m/z (ESI)
calcd for C14H13O (MþH)þ 197.0960, found 197.0961.
4.2.3. (4-Methoxyphenyl)(phenyl)methanone (2c).17 White solid;
yield: 71%; mp 61.2e62.0 ꢀC; 1H NMR (400 MHz, CDCl3)
d: 7.80 (d,
J¼8.4 Hz, 2H), 7.73 (d, J¼8.0 Hz, 2H), 7.51e7.45 (m, 3H), 6.96 (d,
J¼8.4 Hz, 2H), 3.91 (s, 3H); 13C NMR (100 MHz, CDCl3)
d
: 197.1,
4.2.11. Dithiophen-2-ylmethanone (2k).18 Yellow solid; yield: 55%;
163.2, 138.2, 132.4, 131.7, 130.0, 129.5, 128.2, 113.6, 55.8; IR (neat
cmꢁ1): 1652 (C]O); LRMS (EI 70 eV) m/z (%): 212 (Mþ, 100);
HRMS m/z (ESI) calcd for C14H13O2 (MþH)þ 213.0909, found
213.0913.
mp 91.2e92.2 ꢀC; 1H NMR (400 MHz, CDCl3)
d
: 8.08 (dd, J¼4.0 Hz,
J¼1.2 Hz, 2H), 7.86 (dd, J¼4.8 Hz, J¼1.2 Hz, 2H), 7.22e7.17 (m, 2H);
13C NMR (100 MHz, CDCl3)
d: 182.8, 138.5, 137.3, 137.0, 128.6; IR
(neat cmꢁ1): 1631 (C]O); LRMS (EI 70 eV) m/z (%): 194 (Mþ, 100);
HRMS m/z (ESI) calcd for C9H7OS2 (MþH)þ 194.9932, found
194.9936.
4.2.4. (4-Florophenyl)(phenyl)methanone (2d).17 White solid; yield:
66%; mp 48.2e49.1 ꢀC; 1H NMR (400 MHz, CDCl3)
d: 7.86e7.83 (m,
2H), 7.78 (d, J¼4.2 Hz, 2H), 7.62 (dd, J¼7.2 Hz, J¼1.2 Hz, 1H), 7.51 (t,
4.2.12. Phenyl(thiophen-2-yl)methanone (2l).33 Yellowish solid;
J¼7.6 Hz, 2H), 7.18 (t, J¼8.6 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d
:
yield: 64%; mp 56.2e57.0 ꢀC; 1H NMR (400 MHz, CDCl3)
d: 7.87 (d,
195.5, 165.5, 162.9, 137.6, 132.7, 132.7, 132.6, 132.4, 132.0, 129.8,
128.3,115.5,115.3; IR (neat cmꢁ1): 1661 (C]O); LRMS (EI 70 eV) m/z
(%): 200 (Mþ, 100); HRMS m/z (ESI) calcd for C13H10FO (MþH)þ
201.0710, found 201.0719.
J¼7.6 Hz, 2H), 7.73 (d, J¼4.8 Hz, 1H), 7.65 (d, J¼3.6 Hz, 1H), 7.61 (t,
J¼7.4 Hz, 1H), 7.51 (t, J¼7.8 Hz, 2H), 7.17 (t, J¼4.4 Hz, 1H); 13C NMR
(100 MHz, CDCl3) d: 188.2, 143.6, 138.1, 134.8, 134.1, 132.2, 129.1,
128.3, 127.9; IR (neat cmꢁ1): 1638 (C]O); LRMS (EI 70 eV) m/z (%):
188 (Mþ, 100); HRMS m/z (ESI) calcd for C11H9OS (MþH)þ 189.0368,
found 189.0361.
4.2.5. (4-Chlorophenyl)(phenyl)methanone (2e).17 White solid;
yield: 55%; mp 75.3e76.2 ꢀC; 1H NMR (400 MHz, CDCl3)
d
: 7.78 (t,
J¼7.2 Hz, 4H), 7.62 (t, J¼7.4 Hz, 1H), 7.50 (dd, J¼7.6 Hz, J¼8.4 Hz,
4.2.13. Phenyl(pyridin-3-yl)methanone (2m).34 White solid; yield:
4H); 13C NMR (100 MHz, CDCl3)
d
: 195.4, 138.8, 137.2, 135.8, 132.6,
62%; mp 37.8e38.6 ꢀC; 1H NMR (400 MHz, CDCl3)
d: 8.97 (s, 1H),
131.4, 129.9, 128.6, 128.3; IR (neat cmꢁ1): 1664 (C]O); LRMS (EI
70 eV) m/z (%): 218 (41), 216 (Mþ, 100); HRMS m/z (ESI) calcd for
8.80 (d, J¼4.0 Hz, 1H), 8.11 (d, J¼7.6 Hz, 1H), 7.81 (d, J¼8.0 Hz, 2H),
7.64 (t, J¼7.2 Hz, 1H), 7.52e7.43 (m, 3H); 13C NMR (100 MHz, CDCl3)
C
13H10ClO (MþH)þ 217.0415, found 217.0410.
d: 194.8, 152.7, 150.8, 137.1, 136.5, 133.1, 133.0, 129.9, 128.5, 123.3; IR
(neat cmꢁ1): 1664 (C]O); LRMS (EI 70 eV) m/z (%): 183 (Mþ, 100);
HRMS m/z (ESI) calcd for C12H10NO (MþH)þ 184.0825, found
184.0831.
4.2.6. (4-Bromophenyl)(phenyl)methanone (2f).17 White solid;
yield: 58%; mp 79.2e80.0 ꢀC; 1H NMR (400 MHz, CDCl3)
: 7.78 (t,
d
J¼4.2 Hz, 2H), 7.69 (dd, J¼2.0 Hz, J¼2.0 Hz, 2H), 7.64e7.58 (m,
3H), 7.51 (t, J¼7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d
: 195.6,
4.2.14. 2-Naphthylphenone (2n).35 White solid; yield: 67%; mp
137.1, 136.3, 132.6, 131.6, 131.5, 129.9, 128.4, 127.5; IR (neat cmꢁ1):
79.4e80.4 ꢀC; 1H NMR (400 MHz, CDCl3)
d: 8.26 (s, 1H), 7.95e7.91
1659 (C]O); LRMS (EI 70 eV) m/z (%): 260 (Mþ, 100), 258 (81);
(m, 4H), 7.87e7.84 (m, 2H), 7.65e7.60 (m, 2H), 7.57e7.50 (m, 3H);