反应详情

A 3-neck, 1-L round bottom flask equipped with an addition funnel, internal thermometer, and N2 inlet at RT was charged with cyclopentenone (16.48 g, 0.20 mol) in 0.5 L of CH2Cl2. Benzyl(methoxymethyl)trimethylsilylmethylamine (5.0 grams, 21 mmol) and trifluoroacetic acid (TFA) (1.07 mL, 13.9 mmol) were added. To this mixture was added additional benzyl(methoxymethyl)-trimethylsilylmethylamine (40 g, 0.168 mol) dropwise via addition funnel over 1 hour with the reaction temperature being maintained below 25° C. (water bath). After the addition was complete, the mixture was stirred for 4 h. The mixture was washed with 1×100 mL 10% Na2CO3. The layers were separated and the organic layer was washed with 1×100 mL 23% NaCl. The organic extract was concentrated under reduced pressure to give an oil. The oil was redissolved in methyl-t-butyl ether (250 mL) and extracted into 1M H3PO4 (200 mL). The aqueous layer was basified with 50% NaOH to pH 12. The product was extracted with methyl-t-butyl ether (250 mL). The layers were separated and the organic layer was washed with 23% NaCl. The layers were separated. The organic layer was charged with acetonitrile (50 mL) and silica gel (10 gms). The mixture was stirred 5 minutes and filtered through a silica gel pad (10 grams). The filtrate was concentrated to give the title compound (35.0 grams, 81.4% of theory), which was carried on to the next step without further purification. MS (ESI/APCI) m/z 216 (M+H)+.

1. additiondropwise via addition funnel over 1 hour with the reaction temperature
2. additionAfter the addition
3. washThe mixture was washed with 1×100 mL 10% Na2CO3
4. customThe layers were separated
5. washthe organic layer was washed with 1×100 mL 23% NaCl
6. extractionThe organic extract
7. concentrationwas concentrated under reduced pressure
8. customto give an oil
9. extractionextracted into 1M H3PO4 (200 mL)
10. extractionThe product was extracted with methyl-t-butyl ether (250 mL)
11. customThe layers were separated
12. washthe organic layer was washed with 23% NaCl
13. customThe layers were separated
14. additionThe organic layer was charged with acetonitrile (50 mL) and silica gel (10 gms)
15. stirringThe mixture was stirred 5 minutes
16. filtrationfiltered through a silica gel pad (10 grams)
17. concentrationThe filtrate was concentrated