Trapping of Active Methylene Intermediates with Alkenes, Indoles or Thiols
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3-(4-Methylphenyl)-2,3-dihydro-1H-naphtho
[2,1-b]pyran
anal. calcd. for C20H17ClO: C 77.79, H 5.55; found: C 77.69,
H 5.46.
8-Bromo-3-methyl-3-phenyl-2,3-dihydro-1H-naphthoACHTUNGTRENNUNG[2,1-
(3c):[7e] White solid, mp 110–1128C; yield: 68% (ethyl ace-
1
tate/petroleum ether=1/5), H NMR (CDCl3): d=2.12–2.24
(m,1H), 2.30–2.39 (m, 1H), 3.07–3.14 (m, 2H), 5.08 (dd, Ja =
2.0 Hz, Jb =10.4 Hz, 1H), 7.14 (d, J=8.8 Hz, 1H), 7.32 (dd,
Ja =8.0 Hz, Jb =16.0 Hz, 2H), 7.38 (t, J=7.2 Hz, 2H), 7.42–
7.49 (m, 3H), 7.62 (d, J=8.8 Hz, 1H), 7.77 (dd, Ja =8.4 Hz,
Jb =12.4 Hz, 2H); 13C NMR: d=21.8, 29.8, 77.5, 113.7,
119.3, 122.1, 123.4, 126.2, 126.4, 127.9, 128.5, 128.6, 129.1,
133.1, 141.6, 152.8.
b]pyran (3h): White solid, mp 68–708C; yield: 63% (ethyl
acetate/petroleum ether=1/3), 1H NMR (CDCl3): d=1.66
(s, 3H), 2.08–2.20 (m, 1H), 2.45–2.60 (m, 2H), 2.89 (dt, Ja =
4.0 Hz, Jb =16.4 Hz, 1H), 7.17 (t, J=7.2 Hz, 1H), 7.25 (dd,
Ja =7.6 Hz, Jb =15.6 Hz, 3H), 7.35–7.52 (m, 5H), 7.82 (s,
1H); 13C NMR: d=19.4, 30.1, 32.5, 78.4, 113.8, 116.8, 120.6,
123.9, 124.9, 127.0, 127.1, 128.5, 129.3, 130.1, 130.3, 131.5,
145.2, 151.8; IR: n=2975, 2927, 1617, 1587, 1497, 1462, 1445,
1392, 1354, 1313, 1264, 1238, 1184, 1163, 1104, 1071, 1027,
962, 874, 807, 762, 699, 598 cmÀ1; anal. calcd. for C20H17BrO:
C 68.00, H 4.85; found: C 68.11, H 4.73.
3-(4-Chlorophenyl)-2,3-dihydro-1H-naphthoACHTNUTRGNE[NUG 2,1-b]pyran
(3d):[7e] White solid, mp 142–1448C; yield: 30% (ethyl ace-
1
tate/petroleum ether=1/4), H NMR (CDCl3): d=2.04–2.16
(m, 1H), 2.26–2.35 (m, 1H), 3.04–3.11 (m, 2H), 5.02 (dd,
Ja =2.4 Hz, Jb =10.4 Hz, 1H), 7.07 (d, J=9.2 Hz, 1H), 7.27–
7.36 (m, 5H), 7.43 (t, J=7.2 Hz, 1H), 7.59 (d, J=8.8 Hz,
1H), 7.73 (t, J=8.8 Hz, 2H); 13C NMR: d=21.6, 29.7, 76.8,
113.5, 119.1, 122.0, 123.5, 126.5, 127.5, 127.9, 128.5, 128.7,
129.1, 133.0, 133.6, 140.1, 152.4.
8-Bromo-3-(4-fluorophenyl)-3-methyl-2,3-dihydro-1H-
naphthoACHTNUTRGNE[NUG 2,1-b]pyran (3i): Gum-like liquid; yield: 64% (ethyl
acetate/petroleum ether=1/3), 1H NMR (CDCl3): d=1.62
(s, 3H), 2.12 (ddd, Ja =5.6 Hz, Jb =10.0 Hz, Jc =16.0 Hz,
1H), 2.43 (dt, Ja =4.4 Hz, Jb =13.6 Hz, 1H), 2.54 (ddd, Ja =
6.0 Hz, Jb =10.4 Hz, Jc =16.8 Hz, 1H), 2.90 (dt, Ja =5.2 Hz,
Jb =16.4 Hz, 1H), 6.92 (t, J=8.8 Hz, 2H), 7.19 (d, J=
8.8 Hz, 1H), 7.31 (dd, Ja =5.6 Hz, Jb =8.8 Hz, 2H), 7.46
(ddd, Ja =2.8 Hz, Jb =8.8 Hz, Jc =20.8 Hz, 3H), 7.82 (d, J=
2.0 Hz, 1H); 13C NMR: d=19.3, 29.9, 32.5, 78.0, 113.6,
115.2, 115.4, 116.9, 120.4, 123.8, 126.6, 126.7, 127.2, 129.4,
130.1, 130.3, 131.5, 140.9, 140.9, 151.6, 160.5, 162.9; IR: n=
3062, 2977, 2929, 2849, 1593, 1505, 1459, 1392, 1355, 1314,
1263, 1235, 1160, 1109, 1095, 1079, 1015, 962, 871, 835, 808,
731, 593 cmÀ1; anal. calcd. for C20H16BrFO: C 64.71, H 4.34;
found: C 64.86, H 4.30.
3-(4-tert-Butylphenyl)-2,3-dihydro-1H-NaphthoACHTUNTRGNEUNG[2,1-
b]pyran (3e): White solid, mp 122–1248C, yield: 60% (ethyl
acetate/petroleum ether=1/6), 1H NMR (CDCl3): d=1.36
(s, 9H), 2.15–2.27 (m, 1H), 2.31–2.38 (m, 1H), 3.11 (dd, Ja =
4.8 Hz, Jb =8.0 Hz, 2H), 5.05 (dd, Ja =2.0 Hz, Jb =10.4, 1H),
7.13 (d, J=8.8 Hz, 1H), 7.32 (t, J=8.0 Hz, 1H), 7.40 (dd,
Ja =8.8 Hz, Jb =10.8 Hz, 4H), 7.46 (t, J=8.0 Hz, 1H), 7.61
(d, J=8.8 Hz, 1H), 7.77 (dd, Ja =8.8 Hz, Jb =15.2 Hz, 2H);
13C NMR: d=21.9, 29.5, 31.5, 34.7, 77.5, 113.7, 119.4, 122.1,
123.3, 125.6, 126.1, 126.4, 127.8, 128.5, 129.1, 133.1, 138.5,
151.0, 152.9; IR: n=2948, 2868, 1620, 1597, 1512, 1465, 1396,
1360, 1261, 1237, 1175, 1108, 1067, 993, 972, 904, 861, 818,
768, 741, 572 cmÀ1; anal. calcd. for C23H24O: C 87.30, H 7.64;
found: C 87.44, H 7.71.
2,6-Dimethyl-3-methoxycarbonyl-6-phenyl-5,6-dihydropyr-
an (5a): Colorless liquid, yield: 69% (heptane/ethyl acetate:
1
4/1), H NMR: d=1.54 (s, 3H), 1.79–1.98 (m, 2H), 2.05–2.24
3-(4-Fluorophenyl)-3-methyl-2,3-dihydro-1H-naphthoACTHNUTRGNEU[GN 2,1-
(m, 1H), 2.25–2.37 (m, 1H), 2.39 (s, 3H), 3.62 (s, 3H), 7.12–
7.29 (m, 3H), 7.29–7.35 (t, J=8.0 Hz, 2H); 13C NMR: d=
19.5, 20.5, 29.3, 32.4, 50.9, 79.5, 100.9, 124.3, 127.0, 128.5,
144.9, 163.7, 168.8; IR: n=2978, 2948, 1706, 1621, 1446,
1434, 1379, 1296, 1278, 1264, 1233, 1186, 1165, 1094, 1086,
1073, 1028, 1012, 957, 762, 698 cmÀ1; HR-MS (ESI): m/z=
247.3097, calcd. for C15H18O3, [M+H+]: 247.3096.
3-Acyl-2,6-dimethyl-6-phenyl-5,6-dihydropyran (5b): Col-
orless liquid, yield: 78% (heptane/ethyl acetate: 2/1),
1H NMR: d=1.55 (s, 3H), 1.85–2.08 (m, 2H), 2.11 (s, 3H),
2.15–2.33 (m, 2H), 2.37 (s, 3H), 7.19–7.27 (m, 3H), 7.32–
7.36 (m, 2H); 13C NMR: d=20.8, 21.3, 29.4, 29.5, 32.6, 79.3,
109.6, 124.2, 127.0, 128.5, 144.7, 163.2, 198.8; IR: n=2980,
2929, 2966, 1668, 1567, 1446, 1375, 1284, 1095, 1073, 945,
766, 699 cmÀ1; HR-MS (ESI): m/z=230.3109, calcd. for
C15H18O2, [M]: 230.3022.
b]pyran (3f): Colorless liquid; Yield: 70% (ethyl acetate/pe-
troleum ether=1/4), 1H NMR (CDCl3): d=1.60 (s, 3H),
2.09 (ddd, Ja =6.0 Hz, Jb =10.4 Hz, Jc =13.6 Hz, 1H), 2.37
(dt, Ja =4.8 Hz, Jb =13.6 Hz, 1H), 2.55 (ddd, Ja =6.0 Hz, Jb =
10.0 Hz, Jc =20.4 Hz, 1H), 2.93 (dt, Ja =4.8 Hz, Jb =16.4 Hz,
1H), 6.88 (dt, Ja =2.4 Hz, Jb =8.8 Hz, 2H), 7.20 (dd, Ja =
4.4 Hz, Jb =9.2 Hz, 1H), 7.22–7.34 (m, 3H), 7.38 (t, J=
8.8 Hz, 1H), 7.63 (t, J=8.4 Hz, 2H), 7.69 (t, J=8.0 Hz, 1H);
13C NMR: d=19.5, 30.0, 32.8, 77.9, 113.5, 115.2, 115.4, 119.5,
122.1, 123.4, 126.4, 126.8, 126.8, 128.2, 128.6, 129.1, 133.1,
141.2, 141.3, 151.4, 160.6, 163.0; IR: n=3062, 2977, 2929,
2847, 1603, 1510, 1466, 1435, 1396, 1319, 1266, 1234, 1160,
1108, 1092, 1015, 965, 921, 888, 868, 835, 812, 771, 746,
687 cmÀ1; anal. calcd. for C20H17FO: C 82.17, H 5.86; found:
C, 82.24, H 5.81.
3-(4-Chlorophenyl)-3-methyl-2,3-dihydro-1H-naphthoACTHNUTRGNEU[GN 2,1-
3-Ethoxycarbonyl-2-[(Ethoxycarbonyl)methyl]-6-methyl-
6-phenyl-5,6-dihydropyran (5c): Colorless liquid, yield: 44%
b]pyran (3g): Colorless liquid, yield: 69% (ethyl acetate/pe-
troleum ether=1/4), 1H NMR (CDCl3): d=1.62 (s, 3H),
2.13 (ddd, Ja =5.6 Hz, Jb =10.6 Hz, Jc =16.0 Hz, 1H), 2.42
(ddd, Ja =4.4 Hz, Jb =5.6 Hz, Jc =13.6 Hz, 1H), 2.57 (ddd,
Ja =6.0 Hz, Jb =10.0 Hz, Jc =16.4 Hz, 1H), 2.96 (dt, Ja =
5.2 Hz, Jb =16.8 Hz, 1H), 7.19 (dd, Ja =3.2 Hz, Jb =9.2 Hz,
3H), 7.25–7.32 (m, 3H), 7.39 (t, J=7.2 Hz, 1H), 7.64 (dd,
Ja =5.2 Hz, Jb =8.0H, 2H), 7.71 (d, J=8.0 Hz, 1H);
13C NMR: d=19.4, 29.9, 32.6, 77.9, 113.4, 119.3, 122.0, 123.4,
126.4, 126.6, 128.1, 128.5, 128.6, 129.0, 132.6, 133.0, 144.0,
151.3; IR: n=2926, 1618, 1594, 1508, 1485, 1465, 1433, 1395,
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(ethyl acetate/petroleum ether=1/3), H NMR (CDCl3): d=
1.23 (t, J=7.2 Hz, 3H), 1.28 (t, J=7.2 Hz, 3H), 1.58 (s, 3H),
1.92 (ddd, Ja =6.4 Hz, Jb =8.0 Hz, Jc =13.6 Hz, 1H), 2.02–
2.18 (m, 2H), 2.39 (dt, Ja =2.0 Hz, Jb =16.8 Hz, 1H), 3.78 (d,
J=16.4 Hz, 1H), 3.90 (d, J=16.4 Hz, 1H), 4.11 (ddd, Ja =
1.2 Hz, Jb =6.8 Hz, Jc =14.0 Hz, 2H), 4.20 (q, J=7.2 Hz,
2H), 7.23–7.28 (m, 1H), 7.32–7.40 (m, 4H); 13C NMR: d=
14.2, 14.3, 19.5, 28.2, 32.7, 40.1, 59.9, 60.8, 80.2, 103.5, 124.4,
127.1, 128.4, 144.9, 158.9, 167.7, 169.8; IR: n=2981, 2934,
1741, 1699, 1628, 1448, 1371, 1265, 1164, 1097, 1030, 969,
1264, 1235, 1159, 1111, 1088, 1009, 975, 817, 745, 685 cmÀ1
;
Adv. Synth. Catal. 2009, 351, 3269 – 3278
ꢄ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3275