The Journal of Organic Chemistry
ARTICLE
1-(4-Chlorophenyl)-2-phenylethane-1,2-dione19 (2g): 76% yield;
3.5 mmol TBN was used; light yellow solid; H NMR (400 MHz,
1-(Furan-2-yl)-2-(thiophen-2-yl)ethane-1,2-dione13a (2p): 68% yield;
2.5 mmol TBN was used; light yellow solid; 1H NMR (400 MHz, CDCl3,
TMS) δ 8.08 (d, J = 3.6 Hz, 1 H), 7.86 (d, J = 4.4 Hz, 1 H), 7.80 (s, 1 H),
7.64 (d, J = 3.6 Hz, 1 H), 7.22 (t, J = 4.4 Hz, 1 H), 6.65 (d, J = 2.8 Hz, 1 H);
13C NMR (100 MHz, CDCl3) δ 181.9, 177.5, 149.4, 137.4, 137.2, 128.7,
124.6, 113.0; HRMS (EI) calcd for C10H6O3S (Mþ) 206.0038, found
206.0046.
1
CDCl3, TMS) δ 8.00 (d, J = 7.6 Hz, 2 H), 7.96 (d, J = 8.8 Hz, 2 H), 7.71
(t, J = 7.6 Hz, 1 H), 7.52ꢀ7.58 (m, 4 H); 13C NMR (100 MHz, CDCl3)
δ 193.8, 193.1, 141.7, 135.0, 132.7, 131.3, 131.2, 129.9, 129.4, 129.0;
HRMS (EI) calcd for C14H9O2Cl (Mþ) 244.0291, found 244.0287.
1-(4-Bromophenyl)-2-phenylethane-1,2-dione7f (2h): 76% yield; 4.5
mmol TBN was used; light yellow solid; 1H NMR (400 MHz, CDCl3,
TMS) δ 7.97 (d, J = 8.4 Hz, 2 H), 7.85 (d, J = 8.0 Hz, 2 H), 7.66 (d, J =
8.4 Hz, 3 H), 7.52 (t, J = 8.0 Hz, 2 H); 13C NMR (100 MHz, CDCl3) δ
193.8, 193.2, 135.0, 132.7, 132.4, 131.7, 131.2, 130.5, 129.9, 129.0;
HRMS (EI) calcd for C14H9O2Br (Mþ) 287.9786, found 287.9784.
1-(3-Bromophenyl)-2-phenylethane-1,2-dione20 (2i): 70% yield; 2.5
mmol TBN was used; light yellow solid; 1H NMR (400 MHz, CDCl3,
TMS) δ 8.13 (s, 1 H), 7.96 (d, J = 7.6 Hz, 2 H), 7.87 (d, J = 8.0 Hz, 1 H),
7.76 (d, J = 7.6 Hz, 1 H), 7.66 (t, J = 7.6 Hz, 1 H), 7.51 (t, J = 7.6 Hz, 2 H),
7.37 (t, J = 8.0 Hz, 1 H); 13C NMR (100 MHz, CDCl3) δ 193.5, 192.8,
137.7, 135.1, 134.6, 132.6, 132.4 (J = 40.0 Hz), 130.6 (J = 6.3 Hz), 129.9
(J = 7.4 Hz), 129.1 (J = 7.4 Hz), 128.6 (J = 5.6 Hz), 123.3 (J = 6.4 Hz);
HRMS (EI) calcd for C14H9O2Br (Mþ) 287.9786, found 287.9788.
1-(4-Iodophenyl)-2-phenylethane-1,2-dione7f (2j): 70% yield; 4.5
mmol TBN was used; light yellow solid; 1H NMR (400 MHz, CDCl3,
TMS) δ 7.96 (d, J = 8.0 Hz, 2 H), 7.86 (d, J = 8.0 Hz, 2 H), 7.63 (t, J = 7.2
Hz, 1 H), 7.49 (t, J = 7.2 Hz, 2 H), 7.29 (d, J = 8.0 Hz, 2 H); 13C NMR
(100 MHz, CDCl3) δ 194.7, 194.3, 146.2, 134.8, 133.0, 130.6, 130.0,
129.8, 129.7, 129.0; HRMS (EI) calcd for C14H9O2I (Mþ) 335.9647,
found 335.9650.
1-(Furan-2-yl)-2-(1H-pyrrol-2-yl)ethane-1,2-dione (2q): 45% yield;
1
3.5 mmol TBN was used; light yellow solid; H NMR (400 MHz,
C2D6SO, TMS) δ 12.33 (s, 1 H), 8.10 (s, 1 H), 7.46 (d, J = 3.2 Hz, 1 H),
7.29 (s, 1 H), 6.90 (s, 1 H), 6.72 (t, J = 2.0 Hz, 1 H), 6.22 (t, J = 2.0 Hz, 1
H); 13C NMR (100 MHz, C2D6SO) δ 180.3 (J = 2.9 Hz), 179.7 (J = 3.1
Hz), 150.7, 149.7, 129.7 (J = 17.7 Hz), 128.3 (J = 15.4 Hz), 124.2, 122.1
(J = 3.2 Hz), 113.7, 111.8 (J = 3.1 Hz); HRMS (EI) calcd for C10H7NO3
(Mþ) 189.0426, found 189.0424.
1,2-Di(thiophen-2-yl)ethane-1,2-dione21 (2r): 84% yield; 3.5 mmol
TBN was used; light yellow solid; 1H NMR (400 MHz, CDCl3, TMS) δ
8.06 (dd, J = 4.0, 0.8 Hz, 2 H), 7.84 (dd, J = 5.2, 1.2 Hz, 2 H), 7.20 (t, J =
4.4 Hz, 2 H); 13C NMR (125 MHz, CDCl3) δ 182.6, 138.8, 137.7,
137.5, 128.9.
1-Phenylpropane-1,2-dione23 (2s): 55% yield; 2.5 mmol TBN was
1
used; light yellow liquid; H NMR (400 MHz, CDCl3, TMS) δ 8.01
(d, J = 8.0 Hz, 2 H), 7.63 (t, J = 7.6 Hz, 1 H), 7.49 (t, J = 7.6 Hz, 2 H), 2.51
(s, 3 H); 13C NMR (100 MHz, CDCl3) δ 200.4, 191.3, 134.5, 131.7,
130.2, 128.8, 26.2.
1-Phenylbutane-1,2-dione24 (2t): 60% yield; 2.5 mmol TBN was
used; light yellow liquid; 1H NMR(400 MHz, CDCl3, TMS) δ7.98 (d, J=
8.4 Hz, 2 H), 7.64 (t, J = 7.6 Hz, 1 H), 7.50 (t, J = 7.8 Hz, 2 H), 2.92 (q, J =
7.2 Hz, 2 H), 1.20 (t, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ
203.8, 192.6, 134.5, 132.0, 130.1, 128.8, 32.1, 6.7.
1-(Naphthalen-2-yl)-2-phenylethane-1,2-dione21 (2k): 70% yield;
1
2.5 mmol TBN was used; light yellow solid; H NMR (400 MHz,
CDCl3, TMS) δ 8.43 (s, 1 H), 8.12 (d, J = 8.4 Hz, 1 H), 8.05 (d, J = 8.0
Hz, 2 H), 7.99 (t, J = 8.8 Hz, 1 H), 7.91 (t, J = 7.2 Hz, 2 H), 7.63ꢀ7.70
(m, 2 H), 7.50ꢀ7.58 (m, 3 H); 13C NMR (100 MHz, CDCl3) δ 194.7,
136.4, 134.9, 133.5, 133.1, 132.3, 130.3, 130.0, 129.9, 129.6, 129.2, 129.0,
128.0, 127.2, 123.6; HRMS (EI) calcd for C18H12O2 (Mþ) 260.0837,
found 260.0839.
13C-Benzyl (Ia): 76% yield; 2.5 mmol TBN was used; light yellow
solid; 1H NMR (500 MHz, CDCl3, TMS) δ 7.97 (d, J = 7.0 Hz, 4 H),
7.64 (t, J = 7.5 Hz, 2 H), 7.49 (t, J = 7.5 Hz, 4 H); 13C NMR (125 MHz,
CDCl3) δ 194.8, 135.1, 133.1 (q, J = 17.9 Hz) 130.0, 129.2; 13C NMR
(125 MHz, CDCl3) δ 194.8 (s, 86 C), 135.1 (s, 2 C), 133.1 (q, J = 7.5 Hz,
2 C), 130.0 (s, 4 C), 129.2 (s, 4 C); HRMS (EI) calcd for C1313CH10O2
(Mþ) 211.0714, found 211.0712.
1-(Naphthalen-1-yl)-2-phenylethane-1,2-dione21 (2l): 78% yield;
1
2.5 mmol TBN was used; light yellow solid; H NMR (400 MHz,
CDCl3, TMS) δ 8.39 (d, J = 8.4 Hz, 1 H), 8.14 (d, J = 8.0 Hz, 1 H), 8.09
(d, J = 8.4 Hz, 2 H), 7.97 (d, J = 7.2 Hz, 2 H), 7.79 (t, J = 8.0 Hz, 1 H),
7.64ꢀ7.71 (m, 2 H), 7.49 ꢀ7.57 (m, 3 H); 13C NMR (100 MHz,
CDCl3) δ 197.2, 194.6, 136.0, 135.1, 134.8, 134.1, 133.3, 130.9, 130.0,
129.5, 129.0, 128.8, 128.6, 127.1, 125.9, 124.4; HRMS (EI) calcd for
C18H12O2 (Mþ) 260.0837, found 260.0835.
’ ASSOCIATED CONTENT
S
Supporting Information. Experimental procedures and
b
full spectroscopic data for all new compounds. This material is
1-Phenyl-2-(1H-pyrrol-2-yl)ethane-1,2-dione22 (2m): 60% yield; 2.5
mmol TBN was used; light yellow solid; 1H NMR (400 MHz, CDCl3,
TMS) δ 10.72 (s, 1 H), 8.16 (d, J = 7.6 Hz, 1 H), 8.07 (d, J = 8.0 Hz, 2 H),
7.61 ꢀ7.68 (m, 1 H), 7.52 (t, J = 8.0 Hz, 2 H), 7.29 (s, 1 H), 7.06 (s, 1 H);
13C NMR (100 MHz, CDCl3) δ 192.8, 171.3, 134.6, 133.7, 133.1, 130.2,
128.8, 128.7, 128.5, 122.6, 129.0, 128.0, 127.2, 123.6; HRMS (ESI) calcd
for C12H9NO2 (Mþ) 199.0633, found 199.0637.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: yhzhang@zju.edu.cn.
1-Phenyl-2-(thiophen-2-yl)ethane-1,2-dione13a (2n): 65% yield; 2.5
mmol TBN was used; light yellow solid; 1H NMR (400 MHz, CDCl3,
TMS) δ 8.02 (d, J = 7.2 Hz, 2 H), 7.82 (d, J = 4.4 Hz, 1 H), 7.78 (d, J =
3.6 Hz, 1 H), 7.64 (t, J = 7.2 Hz, 1 H), 7.49 (t, J = 7.6 Hz, 2 H), 7.16 (t, J =
4.4 Hz, 1 H); 13C NMR (100 MHz, CDCl3) δ 198.1, 191.6, 143.1, 134.4,
133.2, 131.7, 130.3, 128.7, 128.6, 128.0, 127.6, 126.9; HRMS (EI) calcd
for C12H8O2S (Mþ) 216.0245, found 216.0247.
’ ACKNOWLEDGMENT
Funding from National Basic Research Program of China
(No. 2011CB936003) and NSFC (No. 20872126, No. 2107216)
is highly acknowledged.
’ REFERENCES
1-(Furan-2-yl)-3-phenylpropane-1,3-dione13a (2o): 45% yield; 2.5
mmol TBN was used; light yellow solid; 1H NMR (400 MHz, CDCl3,
TMS) δ 8.02 (d, J = 7.2 Hz, 2 H), 7.83 (d, J = 4.4 Hz, 1 H), 7.78 (d, J =
4.4 Hz, 1 H), 7.66 (t, J = 7.2 Hz, 1 H), 7.51 (t, J = 7.2 Hz, 2 H), 7.18 (t, J =
4.4 Hz, 1 H); 13C NMR (100 MHz, CDCl3) δ 191.4, 188.2, 155.4, 135.5,
134.7, 134.3, 130.7, 130.1, 129.3, 128.8, 128.5, 128.4; HRMS (EI) calcd
for C12H8O3 (Mþ) 200.0473, found 200.0475.
(1) (a) Hoyos, P.; Sinisterra, J.-V.; Molinari, F.; Alcꢀantara, A. R.;
Doínguez De María, P. Acc. Chem. Res. 2010, 43, 288. (b) Furusawa, T.;
Kawano, M.; Fujita, M. Angew. Chem., Int. Ed. 2007, 46, 5717. (c) Koike,
T.; Murata, K.; Ikariya, T. Org. Lett. 2000, 2, 3833. (d) McKenna, J. M.;
Halley, F.; Souness, J. E.; McLay, I. M.; Pickett, S. D.; Collis, A. J.; Page,
K.; Ahmed, I. J. Med. Chem. 2002, 45, 2173. (e) Deng, X.; Mani, N. S.
Org. Lett. 2006, 8, 269. (f) Hui, X.; Desrivot, J.; Bories, C.; Loiseau, P. M.;
5736
dx.doi.org/10.1021/jo200840y |J. Org. Chem. 2011, 76, 5732–5737