The Journal of Organic Chemistry
Article
NMR (CDCl3, 500 MHz) δ 7.96−8.00 (m, 2H), 7.55−7.60 (m, 1H),
7.42−7.50 (m, 2H), 3.83 (t, 2H, J = 2.52 Hz), 3.61 (t, 2H, J = 6.50
Hz), 2.37−2.42 (m, 2H), 1.87−1.96 (m, 2H); 13C NMR (CDCl3, 125
MHz) δ 192.7, 134.4, 132.5, 127.6, 127.5, 82.7, 72.4, 42.6, 30.3, 29.8,
15.3.
[(MH)+, calcd for C15H19O 215.1430]. Data for 3i: 1H NMR (CDCl3,
500 MHz) δ 7.31−7.35 (m, 2H), 7.22−7.26 (m, 3H), 3.87 (s, 2H),
3.26 (t, 2H, J = 2.43 Hz), 2.20−2.24 (m, 2H), 1.31−1.47 (m, 4H),
0.92 (t, 3H, J = 7.30 Hz); 13C NMR (CDCl3, 125 MHz) δ 197.6,
133.8, 128.4, 127.6, 126.1, 83.0, 72.3, 47.2, 32.6, 29.7, 20.9, 17.4, 12.5.
Data for 1-(4-nitrophenyl)octa-2,3-dien-1-one (2j)/1-(4-
nitrophenyl)oct-3-yn-1-one (3j): 86 mg (70%); yellow oil; 2j:3j =
5:1). Data for 2j: 1H NMR (CDCl3, 500 MHz) δ 8.28 (d, 2H, J = 8.78
Hz), 7.96 (d, 2H, J = 8.78 Hz), 6.28−6.32 (m, 1H), 5.62−5.68 (m,
1H), 2.12−2.20 (m, 2H), 1.34−1.45 (m, 2H), 1.23−1.33 (m, 2H),
0.87 (t, 3H, J = 7.35 Hz); 13C NMR (CDCl3, 125 MHz) δ 214.8,
191.0, 142.7, 137.1, 129.5, 123.4, 95.8, 94.6, 30.8, 27.3, 22.0, 13.7; IR
(neat) 2957, 2930, 2860, 1945, 1732, 1661, 1601, 1318, 1272, 1106,
854 cm−1; HRMS-CI m/z 246.1127 [(MH)+, calcd for C14H16NO3
246.1126]. Data for 3j: 1H NMR (CDCl3, 500 MHz) δ 8.32 (d, 2H, J
= 8.78 Hz), 8.18 (d, 2H, J = 8.78 Hz), 3.83 (t, 2H, J = 2.45 Hz), 2.12−
2.20 (m, 2H), 1.34−1.45 (m, 2H), 1.23−1.33 (m, 2H), 0.87 (t, 3H, J =
7.35 Hz); 13C NMR (CDCl3, 125 MHz) δ 192.7, 134.4, 132.5, 127.6,
127.5, 82.7, 72.4, 42.6, 30.3, 29.8, 15.3.
Data for 1-(4-bromophenyl)octa-2,3-dien-1-one (2k)/1-(4-
bromophenyl)oct-3-yn-1-one (3k): 121 mg (87%); yellow liquid;
2k:3k = 4:1. Data for 2k: 1H NMR (CDCl3, 500 MHz) δ 7.72 (d, 2H,
J = 8.50 Hz), 7.56 (d, 2H, J = 8.50 Hz), 6.26−6.30 (m, 1H), 5.57−5.64
(m, 1H), 2.12−2.22 (m, 2H), 1.36−1.47 (m, 2H), 1.27−1.36 (m, 2H),
0.88 (t, 3H, J = 7.30 Hz); 13C NMR (CDCl3, 125 MHz) δ 213.0,
190.0, 135.4, 130.4, 129.1, 126.4, 94.2, 92.9, 29.8, 26.3, 21.0, 12.7; IR
(neat) 2957, 2930, 2871, 1947, 1733, 1652, 1568, 1428, 1261, 1071,
807 cm−1; HRMS-CI m/z 279.0378 [(MH)+, calcd for C14H16BrO
279.0379]. Data for 3k: 1H NMR (CDCl3, 500 MHz) δ 7.86 (d, 2H, J
= 8.50 Hz), 7.60 (d, 2H, J = 8.50 Hz), 3.76 (t, 2H, J = 2.40 Hz), 2.10−
2.22 (m, 2H), 1.36−1.47 (m, 2H), 1.27−1.36 (m, 2H), 0.87 (t, 3H, J =
7.30 Hz); 13C NMR (CDCl3, 125 MHz) δ 192.0, 133.2, 130.8, 129.1,
127.5, 85.2, 70.8, 30.0, 29.6, 20.8, 17.5, 12.5.
Data for methyl 7-oxo-7-phenylhepta-4,5-dienoate (2d)/methyl
7-oxo-7-phenylhept-4-ynoate (3d): 101 mg (88%); yellow oil; 2d:3d
1
= 5:1. Data for 2d: H NMR (CDCl3, 500 MHz) δ 7.84−7.88 (m,
2H), 7.51−7.55 (m, 1H), 7.40−7.45 (m, 2H), 6.37−6.45 (m, 1H),
5.65−5.73 (m, 1H), 3.63 (s, 3H), 2.43−2.49 (m, 4H); 13C NMR
(CDCl3, 125 MHz) δ 213.4, 191.2, 172.7, 137.5, 132.7, 128.6, 128.3,
94.6, 93.8, 51.7, 32.8, 22.8; IR (neat) 2957, 2939, 1945, 1694, 1653,
1448, 1211, 687 cm−1; HRMS-CI m/z 231.1011 [(MH)+, calcd for
1
C14H15O3 231.1016]. Data for 3d: H NMR (CDCl3, 500 MHz) δ
7.95−7.98 (m, 2H), 7.54−7.58 (m, 1H), 7.44−7.48 (m, 2H), 3.79−
3.82 (m, 2H), 3.65 (s, 3H), 2.50−2.53 (m, 4H); 13C NMR (CDCl3,
125 MHz) δ 193.4, 172.4, 135.4, 133.5, 128.6, 128.4, 83.7, 63.9, 51.7,
33.3, 30.8, 14.8.
Data for 2-(6-oxo-6-phenylhexa-3,4-dien-1-yl)isoindoline-1,3-
dione (2e)/2-(6-oxo-6-phenylhex-3-yn-1-yl)isoindoline-1,3-dione
(3e): 128 mg (81%); yellow glue; 2e:3e = 5:1. Data for 2e: 1H
NMR (CDCl3, 500 MHz) δ 7.73−7.83 (m, 4H), 7.68−7.72 (m, 2H),
7.43−7.49 (m, 1H), 7.36−7.41 (m, 2H), 6.26−6.32 (m, 1H), 5.56−
5.64 (m, 1H), 3.79 (t, 2H, J = 7.20 Hz), 2.50−2.63 (m, 2H); 13C
NMR (CDCl3, 125 MHz) δ 213.8, 191.3, 168.1, 137.4, 134.0, 133.9,
133.4, 132.6, 131.9, 128.6, 128.3, 123.3, 94.2, 91.4, 36.9, 27.2; IR
(neat) 2957, 2923, 2859, 1947, 1701, 1694, 1668, 1653, 1448, 1332,
753, 688 cm−1; HRMS-CI m/z 318.1126 [(MH)+, calcd for
1
C20H16NO3 318.1125]. Data for 3e: H NMR (CDCl3, 500 MHz) δ
7.90−7.93 (m, 2H), 7.80−7.83 (m, 2H), 7.69−7.72 (m, 2H), 7.51−
7.55 (m, 1H), 7.38−7.43 (m, 2H), 3.83 (t, 2H, J = 7.20 Hz), 3.76 (t,
2H, J = 2.42 Hz), 2.50−2.63 (m, 2H); 13C NMR (CDCl3, 125 MHz) δ
193.3, 168.0, 136.9, 133.9, 133.4, 132.0, 128.5, 123.3, 81.6, 74.5, 36.7,
30.8, 18.9.
Data for 1-(p-tolyl)octa-2,3-dien-1-one (2l)/1-(p-tolyl)oct-3-yn-1-
1
Data for 3-cyclohexylidene-1-phenylprop-2-en-1-one (2f): 82 mg
(77%); yellow liquid; 1H and 13C NMR spectra for this compound are
consistent with previously reported literature data;21c 1H NMR
(CDCl3, 500 MHz) δ 7.79−7.84 (m, 2H), 7.49−7.54 (m, 1H),
7.38−7.45 (m, 2H), 6.11−6.14 (m, 1H), 2.17−2.25 (m, 4H), 1.58−
1.65 (m, 2H), 1.46−1.58 (m, 4H); 13C NMR (CDCl3, 125 MHz) δ
209.5, 193.4, 138.0, 133.1, 128.8, 128.0, 105.5, 92.7, 30.1, 26.3, 25.6; IR
(neat) 2956, 2869, 1946, 1651, 1598, 1447, 1272, 1022, 695 cm−1;
HRMS-CI m/z 213.1282 [(MH)+, calcd for C15H17O 213.1274].
Data for 1-cyclohexylidenepent-1-en-3-one (2g): 52 mg (63%);
pale yellow liquid; 1H NMR (CDCl3, 500 MHz) δ 5.57−5.61 (m, 1H),
2.53−2.62 (m, 2H), 2.15−2.31 (m, 4H), 1.57−1.75 (m 6H), 1.08 (t,
3H, J = 7.50 Hz); 13C NMR (CDCl3, 125 MHz) δ 202.9, 193.4, 128.3,
106.4, 94.9, 32.0, 30.2, 26.9, 25.7, 8.8; IR (neat) 2930, 2854, 1949,
1446, 1274, 1212, 686 cm−1; HRMS-CI m/z 165.1284 [(MH)+, calcd
for C11H17O 165.1275].
one (3l): 79 mg (74%); yellow liquid; 2l:3l = 1:1. Data for 2l: H
NMR (CDCl3, 500 MHz) δ 7.78 (d, 2H, J = 8.47 Hz), 7.23 (d, 2H, J =
8.47 Hz), 6.32−6.36 (m, 1H), 5.57−5.62 (m, 1H), 2.40 (s, 3H), 2.11−
2.23 (m, 2H), 1.40−1.51 (m, 2H), 1.29−1.40 (m, 2H), 0.87 (t, 3H, J =
7.20 Hz); 13C NMR (CDCl3, 125 MHz) δ 212.5, 190.3, 142.2, 134.2,
127.9, 127.7, 93.8, 92.8, 29.9, 26.4, 21.0, 20.6, 12.5; IR (neat) 2954,
2872, 1947, 1668, 1601, 1458, 1258, 1206, 1028, 855 cm−1; HRMS-CI
1
m/z 215.1427 [(MH)+, calcd for C15H19O 215.1430]. Data for 3l: H
NMR (CDCl3, 500 MHz) δ 7.89 (d, 2H, J = 8.65 Hz), 7.26 (d, 2H, J =
8.65 Hz), 3.79 (t, 2H, J = 2.49 Hz), 2.41 (s, 3H), 2.11−2.23 (m, 2H),
1.40−1.51 (m, 2H), 1.29−1.40 (m, 2H), 0.88 (t, 3H, J = 7.20 Hz); 13C
NMR (CDCl3, 125 MHz) δ 192.6, 143.2, 132.1, 128.2, 127.7, 84.6,
71.3, 29.8, 29.7, 20.8, 20.6, 17.5, 12.5.
Data for 1-(4-methoxyphenyl)octa-2,3-dien-1-one (2m)/1-(4-
methoxyphenyl)oct-3-yn-1-one (3m): 93 mg (81%); yellow liquid;
1
2m:3m = 2:1. Data for 2m: H NMR (CDCl3, 500 MHz) δ 7.88 (d,
2H, J = 8.70 Hz), 6.90 (d, 2H, J = 8.70 Hz), 6.31−6.36 (m, 1H), 5.55−
5.61 (m, 1H), 3.85 (s, 3H), 2.12−2.22 (m, 2H), 1.40−1.48 (m, 2H),
1.30−1.39 (m, 2H), 0.88 (t, 3H, J = 7.34 Hz); 13C NMR (CDCl3, 125
MHz) δ 213.1, 190.0, 163.2, 130.9, 130.6, 113.5, 94.8, 93.5, 55.4, 30.9,
27.4, 22.0, 13.9; IR (neat) 2957, 2933, 2871, 1948, 1717, 1601,1258,
1169, 1028, 865, 633 cm−1; HRMS-CI m/z 231.1385 [(MH)+, calcd
for C15H19O2 231.1380]. Data for 3m: 1H NMR (CDCl3, 500 MHz) δ
7.97 (d, 2H, J = 8.60 Hz), 6.94 (d, 2H, J = 8.05 Hz), 3.73−3.76 (m,
2H), 3.85 (s, 3H), 2.12−2.22 (m, 2H), 1.40−1.48 (m, 2H), 1.30−1.39
(m, 2H), 0.87 (t, 3H, J = 7.34 Hz); 13C NMR (CDCl3, 125 MHz) δ
192.7, 163.7, 130.9, 128.6, 113.7, 85.5, 72.6, 55.4, 30.8, 30.7, 21.9, 18.5,
13.6.
General Procedure C: Synthesis of Furan Derivatives with
CuCl. To a suspension of CuCl (0.02 mmol, 1 mol %, 2 mg) with dry
dichloromethane (3 mL) was added β-chlorovinyl ketones (2 mmol)
followed by triethylamine (2.2 mmol, 0.3 mL) under argon at ambient
temperature. The resulting solution was stirred for 18 h at this
temperature, after which it was concentrated under reduced pressure
and purified by column chromatography on silica gel (1−2% ethyl
acetate in hexanes) to give furans in 80−95% yields.
Data for deca-4,5-dien-3-one (2h)/dec-5-yn-3-one (3h): 51 mg
(68%); pale yellow liquid. Data for 2h: 1H NMR (CDCl3, 500 MHz) δ
5.69−5.73 (m, 1H), 5.56−5.62 (m, 1H), 2.55−2.62 (m, 2H), 2.12−
2.19 (m, 2H), 1.42−1.49 (m, 2H), 1.34−1.42 (m, 2H), 1.07 (t, 3H J =
7.46 Hz), 0.91 (t, 3H, J = 7.20 Hz); 13C NMR (CDCl3, 125 MHz) δ
211.5, 201.1, 95.9, 94.3, 31.2, 30.0, 26.4, 21.3, 12.7, 7.58; IR (neat)
2957, 2923, 2869, 1946, 1443, 1271, 1022, 993 cm−1; HRMS-CI m/z
153.1286 [(MH)+, calcd for C10H17O 153.1274]. Data for 3h: 1H
NMR (CDCl3, 500 MHz) δ 3.20 (t, 2H, J = 2.60 Hz), 2.60−2.65 (m,
2H), 2.18−2.24 (m, 2H), 1.42−1.49 (m, 2H), 1.32−1.42 (m, 2H),
1.05 (t, 3H, J = 7.12 Hz), 0.88 (t, 3H, J = 7.20 Hz); 13C NMR (CDCl3,
125 MHz) δ 205.5, 82.6, 71.4, 33.5, 32.9, 29.8, 21.6, 17.4, 12.5, 6.7.
Data for 1-phenylnona-3,4-dien-2-one (2i)/1-phenylnon-4-yn-2-
1
one (3i): 83 mg (78%); yellow liquid; 2i:3i = 10:1. Data for 2i: H
NMR (CDCl3, 500 MHz) δ 7.28−7.33 (m, 2H), 7.18−7.24 (m, 3H),
5.74−5.79 (m, 1H), 5.63−5.68 (m, 1H), 3.87 (s, 2H), 2.06−2.19 (m,
2H), 1.31−1.47 (m, 4H), 0.91 (t, 3H, J = 7.30 Hz); 13C NMR
(CDCl3, 125 MHz) δ 212.4, 197.5, 133.9, 128.3, 127.4, 125.7, 96.2,
94.8, 44.7, 29.6, 26.4, 21.2, 12.7; IR (neat) 2955, 2927, 2860, 1946,
1733, 1652, 1598, 1273, 1099, 710 cm−1; HRMS-CI m/z 215.1431
11142
dx.doi.org/10.1021/jo302253c | J. Org. Chem. 2012, 77, 11132−11145