تفاعل #12014

ord-90af6704e9c3417f9f4a191d574bb4d4

ظروف التفاعل

الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

  1. 1
    درجة الحرارةwas heated
  2. 2
    درجة الحرارةto reflux for 2 h
  3. 3
    workup.ADDITIONwas added
  4. 4
    درجة الحرارةThe mixture was heated
  5. 5
    درجة الحرارةto reflux for 16 h
  6. 6
    درجة الحرارةthen cooled to room temperature
  7. 7
    أخرىthe phases were separated
  8. 8
    استخلاصThe aqueous phase was extracted three times with ethyl acetate
  9. 9
    غسيلthe combined organic layers were washed with 1M aqueous sodium hydroxide solution and brine
  10. 10
    تجفيفdried over magnesium sulfate
  11. 11
    ترشيحfiltered
  12. 12
    أخرىevaporated
  13. 13
    أخرىThe residue was purified by chromatography on silica gel (0.032–0.063 mm) with n-hexane as eluant

الإجراء التجريبي

A suspension of 150.0 mg (1.23 mmol) 9-borabicyclo[3.3.1]nonane and 47 μl (0.62 mmol) propargyl bromide in 1 ml tetrahydrofuran was heated to reflux for 2 h. The mixture was cooled to room temperature then 0.61 ml (1.83 mmol) of a degassed 3M sodium hydroxide solution was added and after 1 h a mixture of 0.20 g (0.54 mmol) (4R,9aR)-6-bromo-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester (Example 5, intermediate b) and 19.0 mg tetrakis(triphenylphosphine)palladium in 1 ml tetrahydrofuran was added. The mixture was heated to reflux for 16 h then cooled to room temperature and poured into water and ethyl acetate; the phases were separated. The aqueous phase was extracted three times with ethyl acetate and the combined organic layers were washed with 1M aqueous sodium hydroxide solution and brine, dried over magnesium sulfate, filtered and evaporated. The residue was purified by chromatography on silica gel (0.032–0.063 mm) with n-hexane as eluant to afford the desired product as a colorless oil (35.2%).

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US07098337B2uspto-grants-2006_08