1734 Bull. Chem. Soc. Jpn., 77, No. 9 (2004)
Radical Reactions with Zirconocene Complexes
140.94. Found: C, 76.81; H, 9.69%. Calcd for C15H22O2: C,
76.88; H, 9.46%.
hydropyran (25f). IR (neat) 2946, 2930 2850, 1726, 1657, 1600,
1580, 1495, 1356, 1203, 870, 728 cmꢂ1; 1H NMR (CDCl3) ꢁ 1.25
(s, 9H), 1.43–1.95 (m, 12H), 1.97–2.09 (m, 1H), 2.34–2.45 (m,
1H), 3.58 (ddd, J ¼ 3:6, 7.2, 10.8 Hz, 1H), 4.02 (ddd, J ¼ 3:6,
7.2, 10.8 Hz, 1H), 4.11 (ddd, J ¼ 4:8, 4.8, 7.8 Hz, 1H), 5.21 (d,
J ¼ 4:8 Hz, 1H); 13C NMR (CDCl3) ꢁ 23.01, 23.08, 25.14,
25.25, 27.20, 30.07, 31.12, 32.57, 38.65, 38.66, 63.25, 75.92,
78.94, 96.18, 98.21. Found: C, 52.14; H, 6.79%. Calcd for
C17H27IO2: C, 52.31; H, 6.97%.
7-Phenylmethyl-2,9-dioxabicyclo[4.3.0]nonane (27, Mixture
of Diastereomers, 57/43). IR (neat) 3022, 2934, 2866, 1604,
1496, 1454, 1252, 1146, 1100, 1054, 1022, 949, 899, 871, 753,
700 cmꢂ1 1H NMR (CDCl3) ꢁ 1.28–1.99 (m, 5H), 2.52–2.88
;
3-Isopropyl-1-prenylindoline (16). IR (neat) 3042, 3022,
2954, 2922, 2866, 1672, 1605, 1491, 1459, 1384, 1249, 1156,
1
1023, 923, 843, 741, 723 cmꢂ1; H NMR (CDCl3) ꢁ 0.87 (d, J ¼
6:9 Hz, 3H), 0.98 (d, J ¼ 6:9 Hz, 3H), 1.71 (s, 3H), 1.74 (s, 3H),
1.97–2.09 (m, 1H), 3.03–3.17 (m, 2H), 3.27–3.37 (m, 1H), 3.67 (d,
J ¼ 6:6 Hz, 2H), 5.27 (t, J ¼ 6:6 Hz, 1H), 6.47 (d, J ¼ 8:1 Hz,
1H), 6.63 (dd, J ¼ 7:5, 7.5 Hz, 1H), 7.04–7.11 (m, 2H); 13C NMR
(CDCl3) ꢁ 17.89, 18.62, 20.42, 25.65, 30.60, 46.42, 46.76, 55.02,
107.09, 117.07, 120.35, 124.51, 127.47, 132.80, 135.19, 152.83.
Found: C, 83.79; H, 10.11%. Calcd for C16H23N: C, 83.68; H,
10.17%.
3-Bromo-2-(1-ethylhexanyloxy)tetrahydropyran (17, Mix-
ture of Diastereomers, 50/50). IR (neat) 2928, 2856, 2726,
1465, 1378, 1354, 1204, 1152, 1126, 1086, 1071, 1022, 946,
(m, 3H), 3.34–3.45 (m, 0.43H), 3.60–3.67 (m, 1H), 3.73–3.90
(m, 2.14H), 4.17 (dd, J ¼ 8:1, 8.1 Hz, 0.43H), 5.03 (d, J ¼ 3:6
Hz, 0.43H), 5.28 (d, J ¼ 3:6 Hz, 0.57H), 7.14–7.31 (m, 5H);
13C NMR (CDCl3) For major isomer: ꢁ 19.41, 23.01, 33.27,
38.62, 42.39, 60.87, 69.80, 101.96, 126.20, 128.38, 128.54,
140.20. For minor isomer: ꢁ 20.60, 22.32, 36.52, 39.39, 43.71,
64.21, 73.52, 102.11, 126.24, 128.51, 128.54, 140.14. Found: C,
76.96; H, 8.39%. Calcd for C14H18O2: C, 77.03; H, 8.31%.
Spiro[2,9-dioxabicyclo[4.3.0]nonane-8,10-cyclohexane] (33).
IR (neat) 2924, 2856, 1472, 1450, 1398, 1360, 1219, 1161,
914, 870, 726 cmꢂ1 1H NMR (CDCl3) ꢁ 0.86–0.96 (m, 6H),
;
1.23–1.63 (m, 11H), 1.81–2.01 (m, 2H), 2.34–2.46 (m, 1H),
3.51–3.63 (m, 2H), 3.92–4.02 (m, 2H), 4.64 (d, J ¼ 5:1 Hz,
1H); 13C NMR (CDCl3) ꢁ 8.81, 9.52, 13.84, 13.84, 22.41, 22.41,
23.76, 23.84, 24.35, 24.90, 25.52, 27.46, 30.77, 30.85, 31.79,
31.86, 32.64, 32.74, 50.21, 50.21, 62.89, 62.95, 79.02, 79.61,
100.09, 100.45. Found: C, 53.17; H, 8.78%. Calcd for
C13H25BrO2: C, 53.25; H, 8.59%.
1
1136, 1092, 997, 962, 914, 876 cmꢂ1; H NMR (CDCl3) ꢁ 1.08
3-Bromo-2-(3-phenyl-2-propenyloxy)tetrahydropyran (25c).
IR (neat) 3022, 2944, 2850, 1949, 1726, 1705, 1657, 1600, 1579,
1495, 1449, 1356, 1203, 869, 730, 691 cmꢂ1; 1H NMR (CDCl3) ꢁ
1.46–1.57 (m, 1H), 1.85–1.99 (m, 2H), 2.34–2.46 (m, 1H), 3.58
(ddd, J ¼ 3:6, 6.3, 11.4 Hz, 1H), 3.94 (ddd, J ¼ 3:6, 7.8, 11.4
Hz, 1H), 4.02 (ddd, J ¼ 4:2, 4.2, 6.6 Hz, 1H), 4.21 (dd,
J ¼ 6:6, 12.9 Hz, 1H), 4.41 (dd, J ¼ 5:7, 12.9 Hz, 1H), 4.70 (d,
J ¼ 4:2 Hz, 1H), 6.29 (ddd, J ¼ 5:7, 6.6, 15.9 Hz, 1H), 6.38 (d,
J ¼ 15:9 Hz, 1H), 7.20–7.41 (m, 5H); 13C NMR (CDCl3) ꢁ
23.16, 30.00, 49.24, 62.47, 68.29, 100.12, 125.13, 126.51,
127.74, 128.52, 132.89, 136.57. Found: C, 56.77; H, 5.79%. Calcd
for C14H17BrO2: C, 56.58; H, 5.77%.
(s, 9H), 1.14–1.92 (m, 14H), 2.79 (ddd, J ¼ 4:2, 6.6, 10.5 Hz,
1H), 3.70 (ddd, J ¼ 1:8, 3.9, 11.4 Hz, 1H), 3.92 (ddd, J ¼ 2:4,
11.4, 11.4 Hz, 1H), 5.08 (s, 1H), 5.18 (d, J ¼ 4:2 Hz, 1H);
13C NMR (CDCl3) ꢁ 22.48, 22.55, 23.47, 25.18, 26.80, 30.78,
33.22, 36.40, 37.44, 39.85, 60.59, 81.40, 98.28, 132.15, 145.78.
NOE (1H diffectrum, 300 Hz, CDCl3): irradiation of ꢁ ¼
2:75{2:84 (CH) enhancement of signals at ꢁ ¼ 1:08 (CH3,
0.32%), ꢁ ¼ 5:18 (CH, 2.2%); irradiation of ꢁ ¼ 5:08 (CH) en-
hancement of signals at ꢁ ¼ 1:14{1:22 (CH2, 2.3%), ꢁ ¼
1:35{1:43 (CH2, 1.6%).
2-(3-Cyclopropyl-2-butenyloxy)-3-iodotetrahydropyran
(3a0). IR (neat) 3078, 2924, 2848, 1659, 1463, 1439, 1382, 1353,
1302, 1202, 1171, 1122, 1021, 942, 866, 814, 694, cmꢂ1; 1H NMR
(CDCl3) ꢁ 0.47–0.68 (m, 4H), 1.41–1.48 (m, 1H), 1.52–1.61 (m,
1H), 1.57 (s, 3H), 1.67–1.81 (m, 1H), 1.92–2.06 (m, 1H), 2.36–
2.46 (m, 1H), 3.58 (ddd, J ¼ 5:1, 6.3, 8.4 Hz, 1H), 3.95–4.07
(m, 3H), 4.24 (dd, J ¼ 6:6, 11.7 Hz, 1H), 4.63 (d, J ¼ 5:1 Hz,
1H), 5.42 (dd, J ¼ 6:6, 6.9 Hz, 1H); 13C NMR (CDCl3) ꢁ 4.52,
13.95, 18.52, 25.39, 29.42, 32.62, 63.28, 64.26, 101.28, 118.20,
141.83. Found: C, 44.69; H, 6.03%. Calcd for C12H19IO2: C,
44.74; H, 5.94%.
Phenylmethyl-d-2,9-dioxabicyclo[4.3.0]nonane (41a, Mix-
ture of Diastereomers, 68/32). IR (neat) 3061, 3026, 2923,
2872, 1736, 1497, 1450, 1250, 1148, 1022, 991, 951, 897, 872,
733, 702 cmꢂ1 1H NMR (CDCl3) ꢁ 1.25–2.00 (m, 5H), 2.52–
;
2.88 (m, 2H), 3.41 (dd, J ¼ 2:7, 10.4 Hz, 0.32H), 3.59–3.68 (m,
1H), 3.72–3.91 (m, 2.36H), 4.17 (dd, J ¼ 1:2, 8.1 Hz, 0.32H),
5.03 (d, J ¼ 3:3 Hz, 0.32H), 5.27 (d, J ¼ 3:9 Hz, 0.68H), 7.13–
7.32 (m, 5H); 13C NMR (CDCl3) For major isomer: ꢁ 19.39,
22.98, 32.90 (t, J ¼ 19:4 Hz), 36.47, 42.29, 60.84, 69.75,
101.92, 126.17, 128.48, 128.52, 140.13. For minor isomer: ꢁ
20.56, 22.28, 38.19, (t, J ¼ 19:1 Hz), 39.25, 43.65, 64.20,
73.47, 102.08, 126.21, 128.35, 128.52, 139.98. Found: C, 76.38;
H + D, 8.56%. Calcd for C14H17DO2: C, 76.68; H + D, 8.73%.
7-(1-Phenyl-3-butenyl)-2,9-dioxabicyclo[4.3.0]nonane (41b,
3-Chloro-2-(3-methyl-2-butenyloxy)tetrahydropyran (25d,
Mixture of Stereoisomers, 60/40).
1734, 1734, 1671, 1438, 1378, 1205, 1132, 1091, 1074, 1013,
950, 873, 730, cmꢂ1 1H NMR (CDCl3) ꢁ 1.44–1.57 (m, 1H),
IR (neat) 2930, 2874,
;
1.69 (s, 3H), 1.76 (s, 3H), 1.78–2.02 (m, 2H), 2.06–2.22 (m,
0.4H), 2.25–2.37 (m, 0.6H), 3.48–3.61 (m, 1H), 3.79–4.02 (m,
2H), 4.07 (dd, J ¼ 6:9, 12.0 Hz, 1H), 4.23 (dd, J ¼ 6:6, 12.0
Hz, 1H), 4.57 (d, J ¼ 4:2 Hz, 0.6H), 4.74 (d, J ¼ 3:0 Hz,
0.4H), 5.36 (dd, J ¼ 6:6, 6.9 Hz, 0.6H), 5.38 (dd, J ¼ 6:6, 6.9
Hz, 0.4H); 13C NMR (CDCl3) For major isomer: ꢁ 17.76, 21.89,
25.59, 28.92, 56.68, 61.89, 64.12, 99.70, 120.15, 137.95. For mi-
nor isomer: ꢁ 17.81, 21.89, 25.51, 28.30, 57.08, 59.17, 63.95,
96.61, 120.30, 137.53. Found: C, 58.40; H, 8.10%. Calcd for
C10H17ClO2: C, 58.68; H, 8.37%.
3-Bromo-2-(3-phenyl-2-propynyloxy)tetrahydropyran (25e).
IR (neat) 2948, 2924, 2852, 1720, 1599, 1490, 1442, 1355, 1204,
;
1133, 1088, 1071, 1029, 967, 868, 755, 690 cmꢂ1 1H NMR
(CDCl3) ꢁ 1.45–1.57 (m, 1H), 1.90–2.05 (m, 2H), 2.35–2.46 (m,
1H), 3.63 (ddd, J ¼ 5:7, 6.0, 11.7 Hz, 1H), 3.93 (ddd, J ¼ 3:3,
8.4, 11.7 Hz, 1H), 4.06 (dt, J ¼ 3:9, 5.7 Hz, 1H), 4.52 (d, J ¼
3:9 Hz, 2H), 4.93 (d, J ¼ 3:9 Hz, 1H), 7.29–7.32 (m, 3H),
7.43–7.48 (m, 2H); 13C NMR (CDCl3) ꢁ 22.48, 29.24, 48.63,
55.35, 62.13, 84.16, 86.47, 99.01, 122.47, 128.26, 128.51,
131.79. Found: C, 57.09; H, 5.21%. Calcd for C14H15BrO2: C,
56.97; H, 5.12%.
Mixture of Diastereomers, 66/34).
2918, 1641, 1604, 1494, 1469, 1454, 1439, 1404, 1278, 1254,
1202, 1149, 1110, 1025, 989, 948, 900, 871, 763, 701 cmꢂ1
IR (neat) 3060, 3024,
3-Bromo-2-[1-(3,3-dimethyl-1-butynyl)cyclohexyloxy]tetra-
;