Water → HCID 21864742, compound

5-Iodo-1,2,3,4-tetrahydro-1,4-methano-naphthalene-2,3-diol (8.33 g, 27.6 mmol) and Et3NBnCl (10 mg) were vigorously stirred in dichloroethane (25 mL) and H2O (75 mL) then treated with sodium periodate (6.17 g, 29.0 mmol). After 1.5 hours, the layers were separated and the aqueous layer extracted with DCE (2×40 mL). The combined organic layer was washed with H2O (4×30 mL) until no reaction to starch iodide paper was observed, then with saturated aqueous NaCl solution (30 mL). The organic layer was dried through a cotton plug and treated with benzyl amine (3.16 mL, 29.0 mmol) and stirred for 2 minutes then transferred to an addition funnel. This solution was added over ˜10 minutes to a vigorously stirred cooled (0° C.) mixture of NaHB(OAc)3 (18.72 g, 88.0 mmol) in DCE (150 mL). After addition was complete, the mixture was stirred without cooling for 2 hours. The mixture was quenched with saturated aqueous Na2CO3 solution (100 mL) and stirred for 1 hour, then the layers were separated and the aqueous layer was extracted with CH2Cl2 (3×50 mL). The combined organic layer was washed with saturated aqueous NaCl solution (50 mL), dried through a cotton plug and concentrated. Chromatography on Silica gel provided an oil (6.3 g, 61%). (TLC 5% ethyl acetate/hexanes Rf 0.10). 1H NMR (400 MHz, CDCl3) δ 7.61 (d, J=8.0 Hz, 1H), 7.28-7.22 (m, 3H), 7.13 (d, J=8.0 Hz, 1H), 6.98-6.94 (m, 3H), 3,58 (AB dd, J=14.2 Hz, 2H), 3.26 (br s, 1H), 3.21 (brs, 1H), 3.04 (brd, J=10.2 Hz, 1H), 2.83 (br d, J=10.2 Hz, 1H), 2.47 (d, J=10.0 Hz, 1H), 2,39 (d, J=10.0 Hz, 1H), 2,34 (m, 1H), 1.72 (d, J=10.5 Hz, 1H). APCI MS m/e 376.0 [(M+1)+].

1. customthe layers were separated
2. extractionthe aqueous layer extracted with DCE (2×40 mL)
3. washThe combined organic layer was washed with H2O (4×30 mL) until no reaction to starch iodide paper
4. customThe organic layer was dried through a cotton plug
5. customthen transferred to an addition funnel
6. additionThis solution was added over ˜10 minutes to
7. stirringa vigorously stirred
8. temperaturecooled
9. additionAfter addition
10. stirringthe mixture was stirred
11. temperaturewithout cooling for 2 hours
12. customThe mixture was quenched with saturated aqueous Na2CO3 solution (100 mL)
13. stirringstirred for 1 hour
14. customthe layers were separated
15. extractionthe aqueous layer was extracted with CH2Cl2 (3×50 mL)
16. washThe combined organic layer was washed with saturated aqueous NaCl solution (50 mL)
17. customdried through a cotton plug
18. concentrationconcentrated

ORD record

ord-8bc04fd1bdbb4052af9b344fe9a008f7

Source dataset

uspto-grants-2003_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06605610B1