Triethylamine → (1S,2R,5S)-2-(azidomethyl)-6,6-dimethylbicyclo[3.1.1]heptane

Temperature

0 °C

((1S,2R,5S)-6,6-dimethylbicyclo[3.1.1]heptan-2-yl)methanol (500 mg,) was dissolved in dichloromethane (15 mL). The solution was chilled in an ice bath and triethylamine (0.633 mL) was added, followed by methanesulfonyl chloride (0.278 mL). The reaction was stirred for 2 hours at 0° C., and was transferred to a separatory funnel and washed with 1N aqueous HCl (15 mL), saturated aqueous NaHCO3 (20 mL) and brine (15 mL), then dried (Na2SO4), filtered and concentrated to give a crude oil, which was dissolved in N,N-dimethylformamide (7.5 mL). Sodium azide (1054 mg) was added and the mixture was heated to 110° C. for 1.5 hours, and was cooled and partitioned between water (30 mL) and ethyl acetate (3×25 mL). The organic extracts were washed with brine (25 mL), dried (Na2SO4), filtered, and concentrated to give a crude oil, which was purified by flash chromatography on silica gel eluting with 50 to 100% dichloromethane in hexanes to provide the title compound.

1. temperatureThe solution was chilled in an ice bath
2. customwas transferred to a separatory funnel
3. washwashed with 1N aqueous HCl (15 mL), saturated aqueous NaHCO3 (20 mL) and brine (15 mL)
4. dry with materialdried (Na2SO4)
5. filtrationfiltered
6. concentrationconcentrated
7. customto give a crude oil, which
8. temperaturethe mixture was heated to 110° C. for 1.5 hours
9. temperaturewas cooled
10. custompartitioned between water (30 mL) and ethyl acetate (3×25 mL)
11. washThe organic extracts were washed with brine (25 mL)
12. dry with materialdried (Na2SO4)
13. filtrationfiltered
14. concentrationconcentrated
15. customto give a crude oil, which
16. customwas purified by flash chromatography on silica gel eluting with 50 to 100% dichloromethane in hexanes

ORD record

ord-a5f853a6fb88454c96003e134b6b5f5e

Source dataset

uspto-grants-2015_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08940737B2