3264
A.H. Cherney, S.E. Reisman / Tetrahedron 70 (2014) 3259e3265
J¼7.0 Hz, 1H), 3.63 (s, 3H), 2.77e2.38 (m, 4H), 1.41 (d, J¼7.0 Hz, 3H);
13C NMR (125 MHz, CDCl3)
209.0, 173.2, 140.4, 128.9, 127.9, 127.2,
residue was purified by silica gel chromatography (2:98 to 20:80
EtOAc/hexanes) to yield 33.7 mg (71% yield) of 3l as a slightly
d
52.9, 51.7, 35.6, 27.9, 17.3; IR (NaCl/thin film): 3062, 3027, 2977,
yellow oil. 1H NMR (500 MHz, CDCl3)
d 10.03 (s, 1H), 8.11e7.98 (m,
2952, 2932, 1739, 1716, 1494, 1453, 1437, 1372, 1356, 1211 cmꢀ1
;
2H), 7.95e7.75 (m, 2H), 7.45e7.12 (m, 5H), 4.67 (q, J¼6.8 Hz, 1H),
HRMS (MM) calcd for [MþH]þ 221.1172, found 221.1173.
1.55 (d, J¼6.9 Hz, 3H); 13C NMR (125 MHz, CDCl3)
d 199.7, 191.5,
140.7, 138.6, 129.7, 129.2, 128.9, 127.7, 127.2, 126.8, 48.6, 19.3; IR
4.5.4. 4-(2-Phenylpropanoyl)benzonitrile (3g). Prepared from S-
phenyl 4-cyanobenzothioate (1g, 47.9 mg, 0.2 mmol). The crude
residue was purified by silica gel chromatography (2:98 to 20:80
EtOAc/hexanes) to yield 40.8 mg (87% yield) of 3g as a slightly
(NaCl/thin film): 3060, 3026, 2975, 2929, 1700, 1684, 1606, 1452,
1219 cmꢀ1
237.0909.
;
HRMS (MM) calcd for [MꢀH]ꢀ 237.0921, found
yellow oil. 1H NMR (500 MHz, CDCl3)
d
8.04e7.94 (m, 2H), 7.71e7.61
(m, 2H), 7.39e7.17 (m, 5H), 4.61 (q, J¼6.8 Hz, 1H), 1.54 (d, J¼6.8 Hz,
3H); 13C NMR (125 MHz, CDCl3)
198.8, 140.4, 139.5, 132.3, 129.3,
4.5.10. 1-(4-Fluorophenyl)-5-phenylhexane-1,4-dione (3m). Prepared
from S-phenyl 4-(4-fluorophenyl)-4-oxobutanethioate (1m, 57.7 mg,
0.2 mmol). The crude residue was purified by silica gel chromatog-
raphy (2:98 to 10:90 EtOAc/hexanes) to yield 50.3 mg (88% yield) of
d
129.1, 127.6, 127.3, 117.9, 115.9, 48.6, 19.3; IR (NaCl/thin film): 3061,
2976, 2930, 2230, 1685, 1600, 1452, 1404, 1218, 1199 cmꢀ1; HRMS
(MM) calcd for [MꢀH]ꢀ 234.0924, found 234.0932.
3m as a slightly yellow oil.1H NMR (500 MHz, CDCl3)
d 8.03e7.92 (m,
2H), 7.41e7.33 (m, 2H), 7.30e7.21 (m, 3H), 7.16e7.05 (m, 2H), 3.90 (q,
J¼7.0 Hz, 1H), 3.28 (ddd, J¼18.1, 7.6, 5.8 Hz, 1H), 3.06 (dt, J¼18.1,
6.0 Hz,1H), 2.88 (ddd, J¼18.2, 7.6, 5.7 Hz, 1H), 2.72 (dt, J¼18.2, 6.0 Hz,
4.5.5. 2-Phenyl-1-(o-tolyl)propan-1-one (3h). Prepared from S-
phenyl 2-methylbenzothioate (1h, 45.7 mg, 0.2 mmol). The crude
residue was purified by silica gel chromatography (2:98 EtOAc/
hexanes) to yield 35.6 mg (79% yield) of 3h as a slightly yellow oil.
1H), 1.44 (d, J¼7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3)
d 209.5, 197.0,
165.7 (d, JCeF¼254.4 Hz), 140.6, 133.1, 130.7 (d, JCeF¼9.1 Hz), 128.9,
127.9, 127.2, 115.6 (d, JCeF¼21.8 Hz), 53.1, 34.8, 32.5,17.4; IR (NaCl/thin
film): 2975, 2913, 1714, 1685, 1597, 1506, 1410, 1231 cmꢀ1; HRMS
(MM) calcd for [MꢀH]ꢀ 283.1140, found 283.1141.
1H NMR (500 MHz, CDCl3)
d
7.53 (d, J¼7.7 Hz, 1H), 7.36e7.06 (m,
8H), 4.53 (q, J¼6.9 Hz, 1H), 2.34 (s, 3H), 1.55 (d, J¼6.9 Hz, 3H); 13C
NMR (125 MHz, CDCl3) 204.6, 140.4, 138.5, 137.8, 131.5, 130.7, 128.8,
127.9, 127.8, 126.9, 125.3, 50.7, 20.8, 18.5; IR (NaCl/thin film): 3061,
3026, 2971, 2929, 2870, 1685, 1600, 1492, 1452, 1220 cmꢀ1; HRMS
(MM) calcd for [MꢀH]ꢀ 238.1128, found 238.1128.
4.5.11. 1-(4-Chlorophenyl)-5-phenylhexane-1,4-dione (3n). Prepared
from S-phenyl 4-(4-chlorophenyl)-4-oxobutanethioate (1n, 61.0 mg,
0.2 mmol). The crude residue was purified by silica gel chromatog-
raphy (2:98 to 10:90 EtOAc/hexanes) to yield 52.8 mg (88% yield) of
4.5.6. 1-(3-Methoxyphenyl)-2-phenylpropan-1-one (3i). Prepared
from S-phenyl 3-methoxybenzothioate (1i, 48.9 mg, 0.2 mmol). The
crude residue was purified by silica gel chromatography (2:98
EtOAc/hexanes) to yield 29.2 mg (61% yield) of 3i as a slightly yellow
3n as a slightly yellow oil. 1H NMR (500 MHz, CDCl3)
d 7.91e7.83 (m,
2H), 7.48e7.22 (m, 7H), 3.89 (q, J¼7.0 Hz, 1H), 3.26 (ddd, J¼18.1, 7.5,
5.8 Hz,1H), 3.04 (dt, J¼18.2, 5.9 Hz,1H), 2.87 (ddd, J¼18.2, 7.6, 5.6 Hz,
1H), 2.72 (dt, J¼18.2, 6.0 Hz, 1H), 1.44 (d, J¼7.0 Hz, 3H); 13C NMR
oil.1H NMR (500 MHz, CDCl3)
d
7.56e7.44 (m, 2H), 7.34e7.25 (m, 5H),
(125 MHz, CDCl3) d 209.5, 197.4, 140.6, 139.5, 134.9, 129.4, 128.9,
7.24e7.15 (m,1H), 7.02 (ddd, J¼8.2, 2.7, 0.9 Hz,1H), 4.67 (q, J¼6.9 Hz,
128.8, 127.9, 127.2, 53.1, 34.8, 32.5, 17.4; IR (NaCl/thin film): 3062,
1H), 3.80 (s, 3H), 1.53 (d, J¼6.8 Hz, 3H); 13C NMR (125 MHz, CDCl3)
3026, 2974, 2913, 1713, 1685, 1590, 1493, 1452, 1400, 1199 cmꢀ1
;
d
200.1,159.7,141.5,137.8,129.4,129.0,127.7,126.9,121.4,119.3,113.1,
HRMS (MM) calcd for [MꢀH]ꢀ 299.0844, found 299.0870.
55.3, 48.0, 19.5; IR (NaCl/thin film): 3062, 3025, 2973, 2930, 2835,
1681,1596,1581, 1488,1451,1426,1263 cmꢀ1; HRMS (MM) calcd for
[MꢀH]ꢀ 239.1078, found 239.1088.
4.5.12. 1-(4-Methoxyphenyl)-4-methylhexan-3-one (3o). Prepared
from S-phenyl 3-(4-methoxyphenyl)propanethioate (1a, 54.5 mg,
0.2 mmol) and Rieke organozinc 4b (0.5 M THF, 0.56 mL, 0.28 mmol).
The crude residue was purified by silica gel chromatography (5:95
EtOAc/hexanes) to yield 41.4 mg (94% yield) of 3o as a slightly yellow
4.5.7. 1-(2-Methoxyphenyl)-2-phenylpropan-1-one (3j). Prepared
from S-phenyl 2-methoxybenzothioate (1j, 48.9 mg, 0.2 mmol). The
crude residue was purified by silica gel chromatography (2:98
EtOAc/hexanes) to yield 19.2 mg (40% yield) of 3j as a slightly yel-
oil. 1H NMR (500 MHz, CDCl3)
d 7.15e7.05 (m, 2H), 6.87e6.76 (m,
2H), 3.78 (s, 3H), 2.83 (t, J¼7.2 Hz, 2H), 2.81e2.66 (m, 2H), 2.41 (h,
low oil. 1H NMR (500 MHz, CDCl3)
d
7.48 (dd, J¼7.6, 1.8 Hz, 1H), 7.39
J¼6.9 Hz,1H),1.71e1.58 (m,1H),1.44e1.29 (m,1H),1.03 (d, J¼6.9 Hz,
(ddd, J¼8.3, 7.3, 1.8 Hz, 1H), 7.34e7.13 (m, 5H), 6.95e6.89 (m, 2H),
3H), 0.83 (t, J¼7.4 Hz, 3H); 13C NMR (125 MHz, CDCl3)
d 213.9, 157.3,
4.75 (q, J¼7.0 Hz, 1H), 3.88 (s, 3H), 1.54 (d, J¼6.9 Hz, 5H); 13C NMR
133.4, 129.2, 113.8, 55.2, 48.0, 43.0, 28.8, 25.82, 15.7, 11.6; IR (NaCl/
thin film): 2964, 2933, 2875, 2835, 1710, 1612, 1513, 1462, 1300,
1247 cmꢀ1; HRMS (MM) calcd for [M]þ 220.1458, found 220.1414.
(125 MHz, CDCl3)
d 204.1, 157.5, 141.3, 135.1, 132.7, 130.4, 128.4,
128.1, 126.6, 120.5, 111.3, 55.3, 51.8, 18.7; IR (NaCl/thin film): 2929,
1736, 1666, 1597, 1485, 1466, 1284, 1245, 1198 cmꢀ1; HRMS (MM)
calcd for [MþH]þ 241.1223, found 241.1223.
4.5.13. 1-(4-Methoxyphenyl)-4-methylpentan-3-one (3p). Prepared
from S-phenyl 3-(4-methoxyphenyl)propanethioate (1a, 54.5 mg,
4.5.8. 1-(4-(Dimethylamino)phenyl)-2-phenylpropan-1-one
(3k). Prepared from S-phenyl 4-(dimethylamino)benzothioate (1k,
51.5 mg, 0.2 mmol). The crude residue was purified by silica gel
chromatography (2:98 to 20:80 EtOAc/hexanes) to yield 24.4 mg
(48% yield) of 3k as a slightly yellow oil. 1H NMR (500 MHz, CDCl3)
0.2 mmol) and Rieke organozinc 4c (0.5 M THF, 0.56 mL,
0.28 mmol). The crude residue was purified by silica gel chroma-
tography (5:95 EtOAc/hexanes) to yield 38.2 mg (92% yield) of 3p as
a slightly yellow oil. 1H NMR (500 MHz, CDCl3)
d 7.13e7.06 (m, 2H),
6.87e6.78 (m, 2H), 3.78 (s, 3H), 2.87e2.78 (m, 2H), 2.78e2.68 (m,
d
7.95e7.85 (m, 2H), 7.36e7.23 (m, 4H), 7.23e7.13 (m, 1H),
2H), 2.56 (hept, J¼7.0 Hz, 1H), 1.06 (d, J¼6.9 Hz, 6H); 13C NMR
6.62e6.55 (m, 2H), 4.64 (q, J¼6.9 Hz, 1H), 3.00 (s, 6H), 1.51 (d,
(125 MHz, CDCl3) d 214.0, 157.8, 133.4, 129.2, 113.8, 55.2, 42.2, 41.0,
J¼6.9 Hz, 3H); 13C NMR (125 MHz, CDCl3)
d
198.3, 153.1, 142.6, 131.0,
28.9, 18.1; IR (NaCl/thin film): 2968, 2933, 2873, 2835, 1710, 1612,
1513, 1465, 1300, 1246 cmꢀ1; HRMS (MM) calcd for [MꢀH]ꢀ
205.1234, found 205.1575.
130.9, 128.7, 126.5, 124.3, 110.6, 46.9, 39.9, 19.6; IR (NaCl/thin film):
3027, 2974, 2928, 2820, 1651, 1615, 1492, 1448, 1234, 1198 cmꢀ1
;
HRMS (MM) calcd for [MþH]þ 254.1539, found 254.1543.
4.5.14. 1-Cyclopentyl-3-(4-methoxyphenyl)propan-1-one
(3q).
4.5.9. 4-(2-Phenylpropanoyl)benzaldehyde (3l). Prepared from S-
phenyl 4-formylbenzothioate (1l, 48.5 mg, 0.2 mmol). The crude
Prepared from S-phenyl 3-(4-methoxyphenyl)propanethioate (1a,
54.5 mg, 0.2 mmol) and Rieke organozinc 4d (0.5 M THF, 0.56 mL,