Réaction #1382677

Équation de réaction

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

Rendement 82.0%

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

Rendement 82.0%

Solvants

DCE

DCE

water

Conditions de réaction

Traitement

1. 1
   ExtractionThe di-aldehyde was extracted with DCE (2×15 mL)
2. 2
   Lavagewashed with water (5×10 mL
3. 3
   Autreuntil no reaction to starch iodide
4. 4
   Lavageaqueous wash),
5. 5
   AutreThe solvent was removed in vacuo
6. 6
   Autrethe residue was quenched with saturated aqueous NaHCO3 solution
7. 7
   ExtractionThe product was extracted with EtOAc (3×30 mL)
8. 8
   Lavagewashed with saturated aqueous NaCl solution (1×30 mL)
9. 9
   Séchagedried over Na2SO4
10. 10
    Filtrationfiltered through a silica pad (2×3 in)
11. 11
    Lavageeluted with 100% EtOAc
12. 12
    Concentrationconcentrated

Mode opératoire

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)+.

Source