Benzylamine → 11-(Phenylmethyl)-3,11-diazatricyclo[7.3.1.02,7]trideca-2,4,6-triene

3-Aza-tricyclo[7.2.1.02,7]dodeca-2(7),3,5-triene-10,11-diol (1.16 g, 6.07 mmol) was stirred in EtOH (40 mL) and was treated with a solution of NaIO4 (1.35 g, 6.07 mmol) in H2O (20 mL). A precipitate forms and the mixture becomes a yellow slurry. After 15 min, the reaction is deemed complete (TLC EtOAc Rf 0.62), diluted with water and extracted with dichloromethane (4×50 mL). The organic layer was washed with H2O (5×50 mL) then dried through a cotton plug and concentrated to an oil. This oil was stirred in DCE (50 mL), treated with benzyl amine (650 mg, 6.07 mmol) then sodium triacetoxyborohydride NaBH(OAc)3 (4.12 g, 19.4 mmol). The mixture was stirred 7 h, then was quenched by addition to saturated sodium carbonate (Na2CO3) solution and EtOAc (˜75 mL each). After stirring 20 min., the layers were separated and the aqueous layer was extracted with EtOAc (2×50 mL). The organic layer was washed with H2O (50 mL) and saturated aqueous NaCl solution (50 mL) then dried over Na2SO4. Filtration and concentration affords an oil, 1.2 g which was purified by chromatography on silica gel eluting with 50% EtOAc/hexanes to provide pure product as an oil, 802 mg (50%). (TLC EtOAc Rf 0.68); 1H NMR (400 MHz, CDCl3) δ 8.30 (dd, J=4.7, 0.6 Hz, 1H), 7.40 (d, J=7.7 Hz, 1H), 7.13–7.07 (m, 4H), 6.85 (m, 2H), 3.35 (AB q, ΔAB=27.2, J=13.8 Hz, 2H), 3.08 (s, 1H), 3.02 (dd, J=17.3, 7.0 Hz, 1H), 2.92 (d, J=10.6 Hz, 1H), 2.81 (d, J=10.6 Hz, 1H), 2.74 (d, J=17.3 Hz, 1H) 3.34 (br d, J=10.6 Hz, 2H), 2.17 (br s, 1H), 1.90 (d, J=3.0 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 160.8, 145.6, 139.2, 134.7, 134.2, 128.1, 128.0, 126.6, 121.0, 62.3, 60.8, 58.9, 38.4, 34.2, 29.8, 28.4; APCl MS m/z 265.1 (M)+.

1. extractionextracted with dichloromethane (4×50 mL)
2. washThe organic layer was washed with H2O (5×50 mL)
3. customthen dried through a cotton plug
4. concentrationconcentrated to an oil
5. stirringThe mixture was stirred 7 h
6. customwas quenched by addition to saturated sodium carbonate (Na2CO3) solution and EtOAc (˜75 mL each)
7. stirringAfter stirring 20 min.
8. customthe layers were separated
9. extractionthe aqueous layer was extracted with EtOAc (2×50 mL)
10. washThe organic layer was washed with H2O (50 mL) and saturated aqueous NaCl solution (50 mL)
11. dry with materialthen dried over Na2SO4
12. filtrationFiltration and concentration
13. customaffords an oil, 1.2 g which
14. customwas purified by chromatography on silica gel eluting with 50% EtOAc/hexanes
15. customto provide pure product as an oil, 802 mg (50%)

ORD record

ord-9d31ea8e44f948268631d8207e889500

Source dataset

uspto-grants-2008_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07456177B2