The Journal of Organic Chemistry
Note
= 244 Hz, 1C), 140.2, 128.1 (d, J = 7.8 Hz, 1C), 115.6 (d, J = 21 Hz,
1C), 49.2, 44.1, 41.2, 33.0, 25.5; GC−MS (EI) m/z 192 (M)+.
3-(4-(Trifluoromethoxy)phenyl)cyclohexanone (2f). Follow-
ing the general procedure, the crude product was purified over a silica
gel column using ethyl acetate/petroleum ether (1/4) giving a
using ethyl acetate/petroleum ether (1/10) giving a colorless oil
(mixture): yield 85%; H NMR (400 MHz, CDCl3) δ 7.42−7.31 (m,
8H), 7.31−7.22 (m, 2H), 4.67 (t, J = 7.6 Hz, 1H), 4.12 (q, J = 7.2 Hz,
2H), 3.15 (d, J = 7.6 Hz, 1H), 1.19 (s, 3H),; 13C NMR (100 MHz,
CDCl3) δ 171.8, 143.5, 128.6, 127.7, 126.6, 60.5, 47.1, 40.9; GC−MS
(EI) m/z 254 (M)+.
1
1
colorless oil: yield 85%; H NMR (400 MHz, CDCl3) δ 7.25 (d, J =
8.4 Hz, 2H), 7.17 (d, J = 8.4 Hz, 2H), 3.11−2.93 (m, 1H), 2.63−2.29
(m, 4H), 2.22−2.00 (m, 2H), 1.91−1.68 (m, 2H); 13C NMR (100
MHz, CDCl3) δ 210.5, 147.9, 143.1, 128.0, 121.3, 48.9, 44.1, 41.1,
32.8, 25.4; 19F NMR (376 MHz, CDCl3) δ −58.4; HR-ESI-MS [M +
Na]+ m/z calcd for C13H13F3NaO2 281.0765, found 281.0764; GC−
MS (EI) m/z 258 (M)+.
1,3,3-Triphenylpropan-1-one (2o). Following the general
procedure, the crude product was purified over a silica gel column
using ethyl acetate/petroleum ether (1/10) giving a white solid
(mixture): yield 86%; 1H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 8.0
Hz, 2H), 7.52−7.02 (m, 15H), 4.82 (t, J = 7.6 Hz, 2H), 3.70 (d, J = 7.6
Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 198.0, 144.2, 137.1, 133.1,
128.6, 128.6, 128.1, 127.9, 126.4, 46.0, 44.8; GC−MS (EI) m/z 286
(M)+.
3-(Naphthalen-2-yl)cyclohexanone5c (2g). Following the gen-
eral procedure, the crude product was purified over a silica gel column
using ethyl acetate/petroleum ether (1/5) giving a colorless oil: yield
3,3-Diphenyl-1-(p-tolyl)propan-1-one21 (2p). Following the
general procedure, the crude product was purified over a silica gel
column using ethyl acetate/petroleum ether (1/10) giving a white
solid (mixture): yield 91%; 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J =
8.0 Hz, 2H), 7.33−7.03 (m, 14H), 4.81 (t, J = 7.6 Hz, 2H), 3.67 (d, J =
7.6 Hz, 2H), 2.32 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 197.6,
144.3, 143.9, 134.6, 129.3, 128.6, 128.2, 127.9, 126.4, 46.0, 44.6, 21.7;
GC−MS (EI) m/z 300 (M)+.
1
70%; H NMR (400 MHz, CDCl3) δ 7.85−7.72 (m, 3H), 7.61 (s,
1H), 7.49−7.38 (m, 3H), 7.34 (d, J = 9.2 Hz, 1H), 3.19−3.06 (m,
1H), 2.72−2.29 (m, 4H), 2.21−2.04 (m, 2H), 1.97−1.71 (m, 2H); 13C
NMR (100 MHz, CDCl3) δ 211.1, 141.8, 133.6, 132.4, 128.4, 127.7,
127.7, 126.3, 125.7, 125.4, 124.8, 48.9, 44.8, 41.3, 32.7, 25.6; GC−MS
(EI) m/z 224 (M)+.
3-Methyl-3-phenylcyclohexanone5d (2h). Following the gen-
eral procedure, the crude product was purified over a silica gel column
using ethyl acetate/petroleum ether (1/5) giving a colorless oil: yield
1-(4-Methoxyphenyl)-3,3-diphenylpropan-1-one21 (2q). Fol-
lowing the general procedure, the crude product was purified over a
silica gel column using ethyl acetate/petroleum ether (1/10) giving a
white solid (mixture): yield 91%; 1H NMR (400 MHz, CDCl3) δ 7.87
(d, J = 8.8 Hz, 2H), 7.92−7.80 (m, 10H), 6.83 (d, J = 8.8 Hz, 2H),
6.83 (t, J = 7.6 Hz, 1H), 3.71 (s, 3H), 3.63 (d, J = 7.6 Hz, 2H); 13C
NMR (100 MHz, CDCl3) δ 196.4, 163.4, 144.3, 130.3, 130.1, 128.5,
127.9, 126.3, 113.7, 55.4, 46.1, 44.3; GC−MS (EI) m/z 316 (M)+.
3-(4-Methoxyphenyl)-1,3-diphenylpropan-1-one18 (2r). Fol-
lowing the general procedure, the crude product was purified over a
silica gel column using ethyl acetate/petroleum ether (1/10) giving a
1
60%; H NMR (400 MHz, CDCl3) δ 7.36−7.27 (m, 4H), 7.24−7.17
(m, 1H), 2.89 (d, J = 14.4 Hz, 1H), 2.44 (d, J = 14.4 Hz, 1H), 2.36−
2.26 (m, 2H), 2.24−2.14 (m, 1H), 1.97−1.81 (m, 2H), 1.74−1.81 (m,
2H), 1.33 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 211.6, 147.6,
128.7, 126.4, 125.7, 53.3, 43.0, 41.0, 38.1, 30.0, 22.2; GC−MS (EI) m/
z 188 (M)+.
3-Methyl-3-phenylcyclopentanone5d (2i). Following the gen-
eral procedure, the crude product was purified over a silica gel column
using ethyl acetate/petroleum ether (1/5) giving a colorless oil: yield
1
1
1
white solid (mixture): yield 82%; H NMR (400 MHz, CDCl3) H
NMR (400 MHz, CDCl3) δ 7.89 (d, J = 8.0 Hz, 2H), 7.53−7.08 (m,
10H), 6.78 (d, J = 8.8 Hz, 2H), 4.77 (t, J = 7.6 Hz, 1H), 3.68 (m, 5H);
13C NMR (100 MHz, CDCl3) δ 198.1, 158.1, 144.6, 137.1, 136.3,
133.1, 128.8, 128.6, 128.6, 128.1, 127.8, 126.3, 114.0, 55.2, 45.2, 44.9;
GC−MS (EI) m/z 316 (M)+.
73%; H NMR (400 MHz, CDCl3) δ 7.37−7.26 (m, 4H), 7.26−7.19
(m, 1H), 2.64 (d, J = 17.6 Hz, 1H), 2.47 (d, J = 17.6 Hz, 1H), 2.43−
2.21 (m, 4H), 1.38 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 218.5,
148.6, 128.6, 126.4, 125.5, 52.3, 43.9, 36.8, 35.9, 29.5; 19F NMR (376
MHz, CDCl3) δ −63.0 Hz; GC−MS (EI) m/z 174 (M)+.
3-Phenylcyclopentanone5c (2j). Following the general proce-
dure, the crude product was purified over a silica gel column using
ethyl acetate/petroleum ether (1/5) giving a colorless oil: yield 91%;
1H NMR (400 MHz, CDCl3) δ 7.38−7.28 (m, 2H), 7.28−7.19 (m,
3H), 3.46−3.33 (m, 1H), 2.71−2.59 (m, 1H), 2.55−2.36 (m, 2H),
2.36−2.21 (m, 2H), 2.05−1.90 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 218.3, 143.1, 128.7, 126.8, 45.8, 42.2, 38.9, 31.2; GC−MS
(EI) m/z 160 (M)+.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H NMR and 13C NMR spectra for all the compounds
reported. ESI-MS/MS for the reaction mechanism. This
material is available free of charge via the Internet at http://
4,4-Diphenylbutan-2-one18 (2k). Following the general proce-
dure, the crude product was purified over a silica gel column using
ethyl acetate/petroleum ether (1/10) giving a colorless oil: yield 95%;
1H NMR (400 MHz, CDCl3) δ 7.29−7.10 (m, 10H), 4.57 (t, J = 7.6
Hz, 1H), 3.13 (d, J = 7.6 Hz, 2H), 2.01 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 206.8, 143.9, 128.6, 127.7, 126.5, 49.6, 46.1, 30.6; GC−MS
(EI) m/z 224 (M)+.
AUTHOR INFORMATION
Corresponding Author
■
Notes
4-(4-Methoxyphenyl)-4-phenylbutan-2-one19 (2l). Following
the general procedure, the crude product was purified over a silica gel
column using ethyl acetate/petroleum ether (1/10) giving a white
solid: yield 91%; 1H NMR (400 MHz, CDCl3) δ 7.28−7.07 (m, 7H),
6.78 (d, J = 8.0 Hz, 2H), 4.52 (t, J = 7.6 Hz, 1H), 3.70 (s, 3H), 3.11 (d,
J = 7.6 Hz, 2H), 2.02 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 207.0,
158.1, 144.3, 136.0, 128.7, 128.6, 127.6, 126.4, 114.0, 55.2, 49.8, 45.3,
30.6; GC−MS (EI) m/z 254 (M)+.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (Project No. 21176039, 20876021, and
20923006) and the Education Department of Liaoning
Province (2009S021).
Methyl 3,3-Diphenylpropanoate20 (2m). Following the general
procedure, the crude product was purified over a silica gel column
using ethyl acetate/petroleum ether (1/10) giving a colorless oil
REFERENCES
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(1) (a) Hawner, C.; Alexakis, A. Chem. Commun. 2010, 46, 7295.
(b) Rossiter, B. E.; Swingle, N. M. Chem. Rev. 1992, 92, 771.
(2) (a) Hayashi, T.; Yamasaki, K. Chem. Rev. 2003, 103, 2829.
(b) Fagnou, K.; Lautens, M. Chem. Rev. 2003, 103, 169. (c) Edwards,
H. J.; Hargrave, J. D.; Penrose, S. D.; Frost, C. G. Chem. Soc. Rev. 2010,
39, 2093. (d) Luo, Y. F.; Carnell, A. J. Angew. Chem., Int. Ed. 2010, 49,
2750.
1
(mixture): yield 82%; H NMR (400 MHz, CDCl3) δ 7.42−7.08 (m,
10H), 4.56 (t, J = 7.6 Hz, 1H), 3.55 (s, 3H), 3.05 (d, J = 7.6 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 172.3, 143.6, 128.7, 127.7, 126.6, 51.7,
47.1, 40.7; GC−MS (EI) m/z 224 (M)+.
Ethyl 3,3-Diphenylpropanoate5c (2n). Following the general
procedure, the crude product was purified over a silica gel column
4852
dx.doi.org/10.1021/jo300654s | J. Org. Chem. 2012, 77, 4849−4853