反应详情

A 250 mL three-neck flask was fitted with a reflux condenser. 125 mL addition funnel, CaCl2 drying tube and nitrogen line. The apparatus was dried by means of a hot air gun and nitrogen purging. THF (150 mL) distilled from Na/benzophenone was added and the flask cooled in an ice-water bath. Titanium trichloride (12 g, 78 mmol) was added rapidly (fumes in air!) followed by lithium aluminum hydride (1.425 g, 37.5 mmol) in portions with vigorous stirring. The cooling bath was removed and the black mixture was allowed to warm to room temperature. Triethylamine (6 mL, 43 mmol) was added dropwise to the stirred suspension and reflux begun. After 1 hour at reflux, a solution of methyl 6-tert-butyldimethylsilyloxy-2-naphthoate (2.38 g, 7.5 mmol) and adamantanone (1.15 g, 7.67 mmol) in 50 mL of dry THF was added dropwise to the refluxing mixture over an 18 hour period. Reflux was continued for an additional 6 hours. The cooled reaction mixture was quenched by careful addition of 10 mL of methanol and 10 mL of water. The mixture was diluted with 50 mL of pentance and passed down a column of florisil (4"×1.5"), eluting with pentane, then 1:1 ether/pentane. If any of the black material passes through the column it may be removed by extracting the organic phase with water. The pooled organic solutions were concentrated on a rotary evaporator producing a yellow oil which was chromatographed on silica with 5% (V/V) ethyl acetate/hexane. The product containing fractions when evaporated left 1.8 g of a yellow oil which afforded 1.27 g of 1c as slightly yellow crystals from cold pentane: mp 97.5°-98° C.; 1H NMR delta 0.250 (s, 6H), 1.024 (s, 9H), 1.80-1.99 (m, 13H), 2.697 (s, 1H), 3.321 (s, 3H), 7.05-7.72 (m, 6H); 13C NMR delta -4.34, 18.27, 25.73, 28.39, 30.28, 32.32, 37.25, 39.13, 39.28, 57.76, 114.78, 122.19, 126.32, 127.74, 128,06, 128.86, 129.44, 130.88, 131.56, 134.00, 143.73, 153.70; MS m/e (rel. intensity) 435 (37, M+1), 434 (100), 377 (18), 345 (5), 188 (6 ), 162 (18), 14 (11), 73 (20). IR (KBr) 2940, 2915, 1630, 1600, 1480, 1265, 1250, 1090, 855, 840 cm-1. ##STR30##

1. customA 250 mL three-neck flask was fitted with a reflux condenser
2. addition125 mL addition funnel, CaCl2 drying tube
3. customThe apparatus was dried by means of a hot air gun and nitrogen purging
4. distillationTHF (150 mL) distilled from Na/benzophenone
5. additionwas added
6. temperaturethe flask cooled in an ice-water bath
7. customThe cooling bath was removed
8. temperaturereflux
9. temperatureAfter 1 hour at reflux
10. temperatureReflux
11. customThe cooled reaction mixture
12. customwas quenched by careful addition of 10 mL of methanol and 10 mL of water
13. additionThe mixture was diluted with 50 mL of pentance
14. washeluting with pentane
15. customIf any of the black material passes through the column it may be removed
16. extractionby extracting the organic phase with water
17. concentrationThe pooled organic solutions were concentrated on a rotary evaporator
18. customproducing a yellow oil which
19. customwas chromatographed on silica with 5% (V/V) ethyl acetate/hexane
20. additionThe product containing fractions when
21. customevaporated
22. waitleft 1.8 g of a yellow oil which