반응 #1382677

반응 방정식

1,4,5,6-Tetrachloro-7,7-dimethoxy-bicyclo[2.2.1]hept-5-ene-2,3-diol

sodium periodate

p-methoxybenzylamine

NaBH(OAc)3

→

title compound

수율 82.0%

1,5,6,7-Tetrachloro-8,8-dimethoxy-3-(4-methoxy-benzyl)-3-aza-bicyclo[3.2.1]oct-6-ene

수율 82.0%

용매

DCE

DCE

water

반응 조건

후처리

1. 1
   추출The di-aldehyde was extracted with DCE (2×15 mL)
2. 2
   세척washed with water (5×10 mL
3. 3
   기타until no reaction to starch iodide
4. 4
   세척aqueous wash),
5. 5
   기타The solvent was removed in vacuo
6. 6
   기타the residue was quenched with saturated aqueous NaHCO3 solution
7. 7
   추출The product was extracted with EtOAc (3×30 mL)
8. 8
   세척washed with saturated aqueous NaCl solution (1×30 mL)
9. 9
   건조dried over Na2SO4
10. 10
    여과filtered through a silica pad (2×3 in)
11. 11
    세척eluted with 100% EtOAc
12. 12
    농축concentrated

실험 절차

1,4,5,6-Tetrachloro-7,7-dimethoxy-bicyclo[2.2.1]hept-5-ene-2,3-diol (1.23 g, 3.80 mmol) and sodium periodate (1.19 g, 3.80 mmol) were stirred vigorously for 1.5 h in DCE (10 mL) and water (10 mL). The di-aldehyde was extracted with DCE (2×15 mL), washed with water (5×10 mL, or until no reaction to starch iodide is observed in the aqueous wash), then filtered through a cotton plug under N2 into a slurry of p-methoxybenzylamine (0.52 mL, 3.99 mmol) and NaBH(OAc)3 (2.58 g, 12.16 mmol) in DCE (10 mL). After 3 h at room temperature the reaction was judged complete by TLC. The solvent was removed in vacuo, and the residue was quenched with saturated aqueous NaHCO3 solution. The product was extracted with EtOAc (3×30 mL), washed with saturated aqueous NaCl solution (1×30 mL), dried over Na2SO4, filtered through a silica pad (2×3 in), eluted with 100% EtOAc and concentrated to yield the title compound as a white solid (1.32 g, 82%). (TLC 30% EtOAc/hexanes Rf 0.65); 1H NMR (400 MHz, CDCl3) δ 7.12 (d, J=8.3 Hz, 2H), 6.81 (d, J=8.3 Hz, 2H), 3.77 (s, 3H), 3.61 (s, 2H), 3.59 (s, 3H), 3.56 (s, 3H), 2.76 (d, J=11.4 Hz, 2H), 2.71 (d, J=11.1 Hz, 2H); GCMS m/z 427 (M)+.

출처