C. Clausen, R. Wartchow, H. Butenschön
FULL PAPER
endo-cis-1,2-Divinylbicyclo[2.2.1]hept-5-ene-2,3-diol (69): GP1, vi-
nyllithium in DEE (0.89 , 8.5 mL, 7.6 mmol), THF (20 mL), bi-
cyclo[2.2.1]hept-5-ene-2,3-dione[89] (300 mg, 2.5 mmol) in THF
217 (3), 215 (3), 202 (3), 179 (24), 178 (100) [anthraceneϩ], 175 (6),
152 (4), 151 (3), 137 (3), 112 (3), 99 (3), 91 (3), 84 (8), 83 (3), 73
(4), 71 (3), 69 (4). Ϫ HRMS (C20H18O2): calcd. 290.130680; found
(10 mL), 30 min. Column chromatography (l 15 cm, 3.5 cm, PE/ 290130554. Ϫ C20H18O2 (290.36): calcd. C 82.73, H 6.25; found C
DEE 3:1) gave 290 mg (1.6 mmol, 66%) of 69, colorless oil. Ϫ IR
(film): ν˜ ϭ 3372 cmϪ1 (s, br, OH), 3068 (w, olefin. CH), 3020 (w,
olefin. CH), 2972 (s, CH), 2880 (w, CH), 1636 (w, CϭC), 1456 (w),
1416 (m), 1356 (m), 1328 (s), 1260 (m), 1196 (m), 1160 (m), 1088
(s, CϪO), 996 (s), 916 (s), 768 (s), 744 (s), 700 (m). Ϫ 1H NMR
(400.1 MHz, CDCl3): δ ϭ 1.61 (td, 2J ϭ Ϫ9.9 Hz, 3J7,1(4) ϭ 1.9 Hz,
1 H, 7-H), 1.69 (d, 1 H, 7-H), 2.53 (s, 2 H, OH), 2.94 [m, 2 H, 1(4)-
H], 5.13 (dd, J ϭ 1.3 Hz, J9,cis-8 ϭ 10.8 Hz, 2 H, 9-H), 5.33 (dd,
3J9,trans-8 ϭ 17.1 Hz, 2 H, 9-H), 5.97 (dd, 2 H, 8-H), 6.36 [t,
3J5(6),1(4) ϭ 1.9 Hz, 2 H, 5(6)-H]. NOE: Irr. at 7-H, obs. at 8-H
(5.3%); irr. at 8-H, obs. at 7-H (2.6%). Ϫ 13C NMR (100.6 MHz,
CDCl3, DEPT): δ ϭ 42.6 (CH2, C-7), 52.5 [CH, C-1(4)], 81.6 [Cq,
C-2(3)], 112.6 (CH2, C-9), 136.4 [CH, C-5(6)], 141.4 (CH, C-8). Ϫ
MS (70 eV, 25 °C): m/z (%) ϭ 178 (3) [Mϩ], 123 (6), 122 (9), 121
(7), 112 (100) [Mϩ Ϫ C5H6], 111 (21), 105 (26), 95 (19), 94 (53)
[Mϩ Ϫ C5H6 Ϫ H4O], 93 (12), 91 (12), 84 (13), 83 (12), 79 (20), 77
(23), 66 (82) [C5H6ϩ], 65 (20). Ϫ C11H14O2 (178.23): calcd. C 74.13,
H 7.92; found C 73.59, H 7.53.
82.50, H 6.19.
rac-2-Hydroxy-3,3,5,5-tetramethyl-2-vinylcyclopentanone (rac-72):
GP1, vinyllithium in DEE (0.99 , 6.0 mL, 5.9 mmol), THF
(20 mL), 3,3,5,5-tetramethylcyclopentane-1,2-dione[91] (300 mg,
1.9 mmol) in THF (15 mL), 1.5 h at Ϫ78 °C. Extraction with
MTBE. Column chromatography (l 14 cm, л 3.5 cm, PE/TBME
3:1) gave 276 mg (1.5 mmol, 78%) of rac-72, colorless solid (m.p.
68 °C). Ϫ IR (film): ν˜ ϭ 3528 cmϪ1 (w, br, OH), 3096 (w, vinyl
CH), 2972 (s, CH), 2940 (m, CH), 2904 (w, CH), 2872 (m, CH),
1740 (s, CO), 1628 (w, vinyl CϭC), 1460 (m), 1388 (w), 1368 (w),
1336 (w), 1308 (w), 1280 (w), 1236 (w), 1184 (w), 1132 (w), 1100
(m), 1044 (m), 1012 (m), 992 (m), 968 (w), 932 (m), 820 (w). Ϫ H
NMR (400.1 MHz, CDCl3): δ ϭ 0.94 (s, 3 H, 10-H or 11-H ), 1.03
(s, 3 H, 10-H or 11-H), 1.17 (s, 3 H, 8-H or 9-H), 1.22 (s, 3 H, 8-
H or 9-H), 1.81 (d, J ϭ 13.6 or 16.2 Hz, 1 H, 4-H), 1.84 (d, 1 H,
4-H), 2.74 (s, 1 H, OH), 5.25 (dd, J ϭ 1.5 Hz, J7,cis-6 ϭ 10.8, 1
H, 7-H), 5.50 (dd, J7,trans-6 ϭ 16.9 Hz, 1 H, 7-H), 5.98 (dd, 1 H,
2
3
1
2
2
3
3
6-H). Ϫ 13C NMR (100.6 MHz, CDCl3, DEPT): δ ϭ 24.0 (CH3,
C-10 ϩ C-11), 27.8 (CH3, C-8 or C-9), 28.1 (CH2, C-8 or C-9),
40.6 (Cq, C-3 or C-5), 41.2 (Cq, C-3 or C-5), 48.7 (CH2, C-4), 86.3
(Cq, C-2), 116.0 (CH2, C-7), 134.4 (CH, C-6), 222.2 (Cq, C-1). Ϫ
MS (70 eV, 25 °C): m/z (%) ϭ183 (2) [Mϩ ϩ 1], 182 (16) [Mϩ], 139
(2), 127 (3), 126 (3), 125 (2), 111 (3), 99 (8), 98 (100), 97 (10), 84
(3), 83 (31), 79 (4), 70 (5), 69 (5). Ϫ HRMS (C11H22O2): calcd.
182.130680; found 182.130692. Ϫ C11H22O2 (182.26): calcd. C
72.49, H 9.95; found C 71.69, H 9.70.
rac-trans-Dibenzo-1,2-divinylbicyclo[2.2.2]octane-2,3-diol (rac-70)
and cis-Dibenzo-1,2-divinylbicyclo[2.2.2]octane-2,3-diol (71): GP1,
vinyllithium in DEE (0.99 , 4.0 mL, 4.0 mmol), THF (20 mL),
5,7-dibenzobicyclo[2.2.2]octane-2,3-dione[90] (300 mg, 1.3 mmol) in
THF (15 mL). After 45 min, further vinyllithium in DEE (0.99 ,
1.3 mL, 1.3 mmol) was added, 2 h at Ϫ78 °C. Column chromato-
graphy (l 14 cm, л 3.5 cm, PE/TBME 3:1). I: 122 mg (0.4 mmol,
33%) of rac-70, colorless solid (m.p. 168 °C). II: 139 mg (0.5 mmol,
37%) of 71, colorless solid. Assignment of the diastereomers was
1
made by comparison of the H NMR spectra with those of other
1,2-divinyl-1,2-diols, including rac-62.
rac-trans-3,3-Dimethyl-1,2-divinyl-1,2-indanediol (rac-73): GP1, vi-
nyllithium in DEE (0.99 , 5.3 mL, 5.2 mmol), THF (20 mL), 3,3-
dimethyl-1,2-indanedione[92] (300 mg, 1.7 mmol) in THF (15 mL),
30 min at Ϫ78 °C, extraction with TBME. Column chromato-
graphy (l 14 cm, л 3.5 cm, PE/TBME 3:1) gave 292 mg (1.3 mmol,
74%) of rac-73, colorless crystals (from petroleum ether, m.p. 70
°C). Ϫ IR (CHCl3): ν˜ ϭ 3600 cmϪ1 (m, OH), 3088 (w, vinyl CH),
3072 (w, arom. CH), 2992 (w, CH), 2964 (m, CH), 2928 (w, CH),
2868 (w), 1632 (w, vinyl CϭC), 1604 (w, CϭC), 1476 (m), 1456 (w),
1408 (w), 1384 (w), 1360 (w), 1320 (m), 1256 (w), 1228 (w), 1176
(w), 1128 (m, CϪO), 1044 (w), 984 (s), 932 (m), 904 (m), 852 (w),
rac-70: IR (CHCl3): ν˜ ϭ 3548 cmϪ1 (m, br, OH), 3072 (m, arom.
CH), 3000 (m, arom. CH), 2952 (m, CH), 1636 (w, vinyl CϭC),
1464 (m), 1412 (m), 1336 (m), 1236 (m), 1180 (m), 1140 (s, CϪO),
1116 (m), 1092 (w), 1052 (m), 996 (s), 928 (s), 568 (w). Ϫ 1H NMR
(400.1 MHz, CDCl3): δ ϭ 2.49 (s, 2 H, OH), 4.20 [s, 2 H, 1(4)-H],
5.01 (m, 2 H, 18(20)-H], 5.33Ϫ5.43 [m, 4 H, 17(19)-H ϩ 18(20)-
H], 7.18 [m, 2 H, 10(15)-H], 7.21 [m, 2 H, 11(14)-H], 7.30 [m, 2 H,
9(16)-H], 7.37 [m, 2 H, 12(13)-H]. Ϫ 13C NMR (100.6 MHz,
CDCl3, DEPT): δ ϭ 57.6 [CH, C-1(4)], 78.3 [Cq, C-2(3)], 112.7
[CH2, C-18(20)], 125.6 (CH), 126.3 (CH), 126.68 (CH), 126.70
(CH), 139.6 (Cq), 139.9 (Cq), 141.1 [CH, C-17(19)]. Ϫ MS (70 eV,
25 °C): m/z (%) ϭ 290 (2) [Mϩ], 235 (3), 217 (3), 215 (3), 179 (24),
178 (100) [anthraceneϩ], 153 (3), 152 (9), 138 (4), 137 (30), 122 (7),
121 (3), 112 (3), 108 (3), 107 (22), 105 (6), 92 (3), 91 (5), 89 (4), 85
(3), 84 (9), 83 (3), 79 (17), 78 (7), 77 (15), 69 (5), 66 (4). Ϫ HRMS
(C20H18O2): calcd. 290.130680; found 290.131012. Ϫ C20H18O2
(290.36): calcd. C 82.73, H 6.25; found C 82.64, H 6.10.
1
556 (w), 540 (w). Ϫ H NMR (400.1 MHz, CDCl3): δ ϭ 1.26 (s, 3
H, CH3), 1.36 (s, 3 H, CH3), 1.58 (s, 1 H, OH), 1.86 (s, 1 H, OH),
2
5.39 (dd, J ϭ 1.8 Hz, J9,cis-8 ϭ 10.9 Hz, 1 H, 9-H), 5.43Ϫ5.50 (m,
3 H, 9-H ϩ 11-H), 6.20 (dd, J8,trans-9 ϭ 17.4 Hz, 1 H, 8-H), 6.40
(dd, J10,cis-11 ϭ 10.9 Hz, J10,trans-11 ϭ 17.4 Hz, 1 H, 10-H),
7.22Ϫ7.28 (m, 2 H, 5-H ϩ 6-H), 7.33Ϫ7.38 (m, 4-H ϩ 7-H). Ϫ
13C NMR (100.6 MHz, CDCl3, DEPT): δ ϭ 21.5 (CH3), 29.4
(CH3), 50.3 (Cq, C-3), 86.6 (Cq, C-1 or C-2), 87.5 (Cq, C-1 or C-
71: IR (CHCl3): ν˜ ϭ 3572 cmϪ1 (m, OH), 3072 (w, arom. CH), 2), 116.1 (CH2, C-9 or C-11), 118.3 (CH2, C-9 or C-11), 123.4 (CH,
3008 (s, arom. CH), 2952 (w, CH), 2928 (w, CH), 1468 (m), 1412 C-4 or C-6), 124.4 (CH, C-4 or C-6), 127.2 (CH, C-5 or C-7), 129.5
(m), 1312 (w), 1296 (w), 1232 (w), 1172 (m, CϪO), 1132 (m, CϪO), (CH, C-5 or C-7), 136.6 (CH, C-8 or C-10), 138.4 (CH, C-8 or C-
996 (s), 972 (m), 932 (m), 628 (m), 604 (w). Ϫ 1H NMR 10), 142.9 (Cq, C-7a), 151.9 (Cq, C-3a). Ϫ MS (70 eV, 50 °C): m/z
(400.1 MHz, CDCl3): δ ϭ 1.52 (s, 2 H, OH), 4.18 [s, 2 H, 1(4)-H],
(%) ϭ 231 (3) [Mϩ ϩ 1], 230 (9) [Mϩ], 215 (14) [Mϩ Ϫ CH3], 212
2
3
5.18 (dd, J ϭ 1.7 Hz, J18,cis-17 ϭ 10.8 Hz, 2 H, 18-H), 5.42 (dd, (9) [Mϩ Ϫ H2O], 198 (10), 197 (53) [Mϩ Ϫ CH3 Ϫ H2O], 188 (17),
3J18,trans-17 ϭ 17.3 Hz, 2 H, 18-H), 5.65 (dd, 2 H, 17-H), 7.17Ϫ7.23 187 (100) [Mϩ Ϫ CH3 Ϫ C2H4], 179 (14), 175 (17), 169 (34), 160
[m, 4 H, 10(11)-H ϩ 14(15)-H], 7.32Ϫ7.38 [m, 4 H, 9(12)-H ϩ (44), 159 (57) [Mϩ Ϫ CH3 Ϫ C2H4 Ϫ C2H4], 157 (49), 155 (23),
13(16)-H]. Ϫ 13C NMR (100.6 MHz, CDCl3, DEPT): δ ϭ 57.5 147 (29), 145 (68), 143 (52),142 (61), 141 (46), 133 (30), 131 (35),
[CH, C-1(4)], 80.8 [Cq, C-2(3)], 114.4 (CH2, C-18), 125.8 (CH), 129 (49), 128 (42), 115 (63), 103 (19), 99 (19), 91 (36), 77 (33). Ϫ
126.0 (CH), 126.67 (CH), 126.71 (CH), 139.3 (Cq), 139.8 (CH), HRMS (C15H18O2): calcd. 230.130680; found 230.130569. Ϫ
140.3 (Cq). Ϫ MS (70 eV, 25 °C): m/z (%) ϭ 290 (1) [Mϩ], 235 (4),
C15H18O2 (230.31): calcd. C 78.23, H 7.88, found C 77.58, H 7.69.
110
Eur. J. Org. Chem. 2001, 93Ϫ113