Rhenium- and Manganese-Catalyzed Insertion of Alkynes
7.2 Hz, 2H), 7.22–7.33 ppm (m, 5H); 13C NMR (100 MHz, CDCl3): d=
13.6, 21.9, 23.7, 25.0, 25.9, 28.2, 37.8, 50.7, 60.4, 127.3, 127.5, 128.3, 135.6,
138.6, 142.8, 170.2, 212.1 ppm; elemental analysis calcd (%) for C19H24O3:
C 75.97, H 8.05; found: C 76.11, H 8.01.
Ethyl (E)-5-oxo-2-(2-phenylethyl)-3-phenyl-2-hexenoate (7b): IR (neat):
n˜ =3062, 3026, 2979, 2927, 1732, 1701, 1599, 1496, 1456, 1356, 1252, 1172,
1026, 911, 701 cmÀ1 1H NMR (400 MHz, CDCl3): d=1.34 (t, J=7.2 Hz,
;
3H), 2.15 (s, 3H), 2.49 (t, J=7.8 Hz, 2H), 2.66 (t, J=7.9 Hz, 2H), 3.81 (s,
2H), 4.24 (q, J=7.2 Hz, 2H), 6.96–7.33 ppm (m, 10H); 13C NMR
(100 MHz, CDCl3): d=14.0, 29.8, 33.1, 35.6, 51.5, 60.6, 125.8, 127.1, 127.4,
128.2, 128.4, 128.5, 128.9, 132.4, 141.4, 144.9, 168.4, 204.7 ppm; elemental
analysis calcd (%) for C22H24O3: C 78.54, H 7.19; found: C 78.44, H 7.42.
Ethyl
boxylate (3m): IR (nujol): n˜ =2923, 2853, 1713, 1675, 1597, 1418, 1376,
1266, 1239, 1129, 1095, 1071, 1046, 966, 916, 844, 766, 700, 599, 574 cmÀ1
(Z)-5,6,9,10-tetrahydro-10-oxo-8-phenylbenzo[8]annulene-7-car-
;
1H NMR (400 MHz, CDCl3): d=0.67 (t, J=7.2 Hz, 3H), 3.00 (t, J=
7.5 Hz, 2H), 3.25 (t, J=7.5 Hz, 2H), 3.70 (q, J=7.2 Hz, 2H), 3.90 (s,
2H), 6.71–6.76 (m, 2H), 7.17–7.19 (m, 3H), 7.25 (d, J=8.1 Hz, 1H), 7.29
(t, J=12.3 Hz, 1H), 7.41–7.48 ppm (m, 2H); 13C NMR (100 MHz,
CDCl3): d=13.2, 30.1, 33.2, 52.8, 60.3, 126.9, 127.0, 127.4, 127.5, 128.1,
130.1, 131.9, 132.4, 137.6, 138.8, 142.2, 142.5, 169.9, 203.8 ppm; elemental
analysis calcd (%) for C21H20O3: C 78.73, H 6.29; found: C 78.48, H 6.24.
Ethyl (E)-5-oxo-3-phenyl-2-hexenoate (7c): IR (neat): n˜ =3060, 2981,
2935, 1707, 1625, 1577, 1447, 1178, 1040, 876, 767, 696, 546 cmÀ1
;
1H NMR (400 MHz, CDCl3): d=1.30 (t, J=7.2 Hz, 3H), 2.28 (s, 3H),
4.19 (q, J=7.2 Hz, 2H), 4.22 (s, 2H), 6.31 (s, 1H), 7.35–7.38 (m, 3H),
7.39–7.43 ppm (m, 2H); 13C NMR (100 MHz, CDCl3): d=14.2, 29.8, 46.8,
60.1, 119.4, 126.5, 128.7, 129.2, 140.8, 152.1, 166.4, 204.7 ppm; elemental
analysis calcd (%) for C14H16O3: C 72.39, H 6.94; found: C 72.26, H 7.10.
Ethyl
boxylate (3m’): IR (nujol): n˜ =2922, 2853, 1712, 1675, 1597, 1418, 1375,
1266, 1239, 1128, 1095, 1071, 1046, 967, 916, 844, 766, 701, 599, 574 cmÀ1
(E)-5,6,7,10-tetrahydro-10-oxo-8-phenylbenzo[8]annulene-7-car-
Ethyl (E)-2-methyl-5-oxo-3,5-diphenyl-2-pentenoate (7d): IR (neat): n˜ =
;
3080, 3060, 2981, 2928, 1732, 1707, 1598, 1492, 1448, 1365, 1332, 1128,
1H NMR (400 MHz, CDCl3): d=0.71 (t, J=7.2 Hz, 3H), 2.24–2.33 (m,
1H), 2.48–2.56 (m, 1H), 2.96 (dt, J=13.2, 3.9 Hz, 1H), 3.17 (dt, J=13.2,
4.8 Hz, 1H), 3.61–3.69 (m, 1H), 3.72–3.80 (m, 1H), 3.85 (dd, J=12.1,
4.8 Hz, 1H), 6.86 (s, 1H), 7.24 (d, J=7.5 Hz, 1H), 7.32–7.40 (m, 4H),
7.40–7.46 (m, 2H), 7.49 (t, J=7.5 Hz, 1H), 7.82 ppm (d, J=7.8 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=13.3, 30.0, 33.0, 45.2, 60.7, 126.8, 127.1,
128.5, 128.9, 129.7, 130.1, 132.7, 135.0, 139.4, 139.7, 140.6, 148.5, 172.0,
193.7 ppm; elemental analysis calcd (%) for C21H20O3: C 78.73; H 6.29;
found: C 78.53, H 6.25.
977, 755, 704, 621 cmÀ1 1H NMR (400 MHz, CDCl3): d=1.17 (t, J=
;
7.2 Hz, 3H), 1.88 (s, 3H), 4.12 (q, J=7.2 Hz, 2H), 4.50 (s, 2H), 7.23–7.48
(m, 8H), 7.94 ppm (d, J=7.8 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=
13.9, 17.3, 46.6, 60.3, 127.0, 127.1, 127.4, 127.85, 127.92, 128.2, 128.3,
128.4, 132.7, 144.7, 168.4, 196.2; elemental analysis calcd (%) for
C20H20O3: C 77.90, H 6.54, found: C 77.91, H 6.66.
Ethyl (E)-3-(4-methoxyphenyl)-2-methyl-5-oxo-2-hexenoate (7e): IR
(neat): n˜ =2980, 2935, 2907, 2838, 1729, 1606, 1515, 1093, 1029, 838, 770,
602, 542 cmÀ1 1H NMR (400 MHz, CDCl3): d=1.31 (t, J=7.2 Hz, 3H),
;
4-Acetyl-3-phenyl-3-cyclooctenone (3n): IR (neat): n˜ =3079, 2931, 2860,
1.86 (s, 3H), 2.16 (s, 3H), 3.80 (s, 3H), 3.86 (s, 2H), 4.20 (q, J=7.2 Hz,
2H), 6.88 (d, J=9.0 Hz, 2H), 7.11 ppm (d, J=8.7 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=14.1, 17.3, 29.6, 51.4, 55.1, 60.3, 113.6, 128.4, 128.9,
134.7, 144.3, 158.7, 168.6, 205.1 ppm; elemental analysis calcd (%) for
C16H20O4: C 69.54, H 7.30; found: C 69.36, H 7.42.
1700, 1575, 1492, 1444, 1353, 1325, 1232, 1124, 1076, 969, 771, 704 cmÀ1
;
1H NMR (400 MHz, CDCl3): d=1.70 (s, 3H), 1.84–1.92 (m, 4H), 2.54 (t,
J=5.4 Hz, 2H), 2.60 (t, J=5.3 Hz, 2H), 3.60 (s, 2H), 7.17–7.19 (m, 2H),
7.29–7.36 ppm (m, 3H); 13C NMR (100 MHz, CDCl3): d=24.5, 27.8, 30.2,
30.8, 42.3, 50.5, 127.9, 128.5, 128.7, 138.2, 141.5, 141.7, 206.9, 210.1; ele-
mental analysis calcd (%) for C16H18O2: C 79.31, H 7.49; found: C 79.18,
H 7.42.
Ethyl (E)-3-(4-methylphenyl)-2-methyl-5-oxo-2-hexenoate (7 f): IR
(neat): n˜ =3022, 2982, 2926, 2871, 1728, 1623, 1512, 1447, 1042, 1021, 826,
769, 548, 519 cmÀ1 1H NMR (400 MHz, CDCl3): d=1.31 (t, J=7.2 Hz,
;
4-Acetyl-3-phenyl-3-cyclononenone (3o): IR (neat): n˜ =3077, 2922, 2853,
3H), 1.84 (s, 3H), 2.16 (s, 3H), 2.34 (s, 3H), 3.86 (s, 2H), 4.21 (q, J=
7.2 Hz, 2H), 7.06 (d, J=8.1 Hz, 2H), 7.16 ppm (d, J=8.1 Hz, 2H);
13C NMR (100 MHz, CDCl3): d=14.2, 17.3, 21.1, 29.7, 51.4, 60.4, 127.5,
127.6, 129.6, 137.1, 139.6, 144.7, 168.7, 205.0; elemental analysis calcd
(%) for C16H20O3: C 73.82, H 7.74; found: C 73.74, H 7.91.
1702, 1448, 1350, 1230, 1151, 1016, 921, 765, 702 cmÀ1
;
1H NMR
(400 MHz, CDCl3): d=1.51–1.54 (m, 2H), 1.59–1.65 (m, 2H), 1.70 (s,
3H),1.79–1.85 (m, 2H), 2.59 (t, J=6.7 Hz, 2H), 2.67 (t, J=6.4 Hz, 2H),
3.56 (s, 2H), 7.29–7.36 ppm (m, 5H); 13C NMR (100 MHz, CDCl3): d=
25.1, 25.2, 25.8, 30.1, 30.7, 42.8, 51.0, 128.2, 128.3, 128.6, 136.7, 142.2,
143.4, 206.9, 211.7;elemental analysis calcd (%)HRMS (ESI): m/z: calcd
for C17H20O2Na ([M+Na]+): 279.1361; found: 279.1367.
Ethyl (E)-3-(4-trifluoromethylphenyl)-2-methyl-5-oxo-2-hexenoate (7g):
IR (neat): n˜ =2988, 2926, 1716, 1653, 1616, 1559, 1325, 1259, 1164, 1128,
1068, 1018, 852 cmÀ1 1H NMR (400 MHz, CDCl3): d=1.32 (t, J=7.2 Hz,
;
4-Acetyl-3-phenyl-3-cyclodecenone (3p): IR (neat): n˜ =3073, 2929, 2860,
3H), 1.82 (s, 3H), 2.19 (s, 3H), 3.89 (s, 2H), 4.23 (q, J=7.2 Hz, 2H), 7.33
(d, J=8.1 Hz, 2H), 7.62 ppm (d, J=8.4 Hz, 2H); 13C NMR (100 MHz,
CDCl3): d=14.0, 17.1, 29.7, 50.7, 60.6, 123.9 (J=271 Hz), 125.3 (J=
3.6 Hz), 127.9, 128.7, 129.4 (J=30.9 Hz), 143.2, 146.4, 168.0, 204.4 ppm;
elemental analysis calcd (%) for C16H17F3O3: C 61.14, H 5.45; found:
C 61.13, H 5.47.
1683, 1463, 1353, 1120, 1068, 761, 704 cmÀ1 1H NMR (400 MHz, CDCl3):
;
d=1.43–1.50 (m, 4H), 1.52–1.58 (m, 2H), 1.74 (s, 3H), 1.75–1.80 (m,
2H), 2.53 (t, J=6.4 Hz, 2H), 2.68 (t, J=6.3 Hz, 2H), 3.58 (s, 2H), 7.25–
7.27 (m, 2H), 7.32–7.34 ppm (m, 3H); 13C NMR (100 MHz, CDCl3): d=
22.4, 24.3, 25.1, 25.8, 28.8, 31.0, 38.8, 50.5, 128.3, 128.4, 128.7, 137.0, 142.0,
144.1, 207.9, 212.4 ppm; HRMS (ESI): m/z: calcd for C18H22O2Na ([M+
Na]+): 293.1518; found: 293.1511.
Ethyl (E)-3-(4-bromophenyl)-2-methyl-5-oxo-2-hexenoate (7h): IR
(neat): n˜ =2982, 2931, 1725, 1488, 1259, 1071, 1011, 834, 768, 730,
535 cmÀ1 1H NMR (400 MHz, CDCl3): d=1.31 (t, J=7.2 Hz, 3H), 1.82
;
General Procedure for the Reaction of Acyclic b-Keto Esters with
Terminal Alkynes
(s, 3H), 2.17 (s, 3H), 3.85 (s, 2H), 4.21 (q, J=7.2 Hz, 2H), 7.07 (d, J=
8.7 Hz, 2H), 7.48 ppm (d, J=8.7 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d=14.1, 17.1, 29.7, 50.8, 60.5, 129.0, 129.2, 131.1, 131.4, 141.4, 143.4,
168.1, 204.5 ppm; elemental analysis calcd (%) for C15H17BrO3: C 55.40,
H 5.27, found: C 55.46, H 5.16.
A mixture of ethyl 2-methylacetoacetate (5a, 72.1 mg, 0.500 mmol), phe-
nylacetylene (2a, 61.3 mg, 0.600 mmol), [ReBr(CO)3ACHTNUTRGNE(UNG thf)]2 (10.6 mg,
0.0125 mmol), and toluene (1.0 mL) was stirred at 808C for 24 h. The
product was isolated by column chromatography on silica gel to give the
mixture of d-keto esters 6a–8a in 92% yield (113 mg, 0.460 mmol).
Ethyl (E)-3-cyclohexenyl-2-methyl-5-oxo-2-hexenoate (7i): IR (neat): n˜ =
2982, 2931, 2858, 1725, 1707, 1355, 1265, 1118, 1028, 920, 769, 549 cmÀ1
;
Ethyl (E)-2-methyl-5-oxo-3-phenyl-2-hexenoate (7a): IR (neat): n˜ =3057,
1H NMR (400 MHz, CDCl3): d=1.28 (t, JJ=7.2 Hz, 3H), 1.57–1.60 (m,
2H), 1.63–1.67 (m, 2H), 1.92 (s, 3H), 1.96–1.99 (m, 2H), 2.05–2.08 (m,
2H), 2.17 (s, 3H), 3.61 (s, 2H), 4.16 (q, J=7.2 Hz, 2H), 5.46 ppm (m,
1H); 13C NMR (100 MHz, CDCl3): d=14.2, 16.7, 21.9, 22.5, 24.8, 26.7,
29.5, 49.0, 60.2, 124.9, 125.7, 139.1, 147.2, 168.8, 205.4 ppm; elemental
analysis calcd (%) for C15H22O3: C 71.97, H 8.86; found: C 71.96, H 8.86.
2982, 2926, 1717, 1701, 1491, 1356, 1259, 1129, 1027, 776, 704, 532 cmÀ1
;
1H NMR (400 MHz, CDCl3): d=1.31 (t, J=7.2 Hz, 3H), 1.83 (s, 3H),
2.17 (s, 3H), 3.87 (s, 2H), 4.21 (q, J=7.2 Hz, 2H), 7.16–7.18 (m, 2H),
7.25–7.27 (m, 1H), 7.33–7.36 ppm (m, 2H); 13C NMR (100 MHz, CDCl3):
d=14.1, 17.2, 29.7, 51.2, 60.4, 127.0, 127.3, 127.4, 127.7, 128.3, 144.7,
168.4, 204.8 ppm; elemental analysis calcd (%) for C15H18O3: C 73.15,
H 7.37; found: C 73.12, H 7.53.
Ethyl (Z)-2-methyl-3-(2-oxopropyl)-2-tridecenoate (7j): IR (neat,
6j+7j): n˜ =2956, 2926, 2855, 1734, 1707, 1616, 1465, 1354, 1098, 862,
768 cmÀ1 1H NMR (400 MHz, CDCl3): d=0.88 (t, J=6.8 Hz, 3H), 1.22
;
Chem. Asian J. 2009, 4, 1424 – 1433
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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