تفاعل #1071913

معادلة التفاعل

(−)-2-(dicyclohexylphosphino)-2′-(dimethylamino)-1,1′-binaphthyl

2-methyl-5-(N-methyl-anilinomethylene)cyclopentanone

4-Bromobenzonitrile

sodium t-butoxide

→

title compound

المردود 51.0%

2-(4-cyanophenyl)-2-methyl-5-(N-methyl-anilinomethylene)-cyclopentanone

المردود 51.0%

المذيبات

Toluene

ظروف التفاعل

المعالجة

1. 1
   أخرىAn oven dried Schlenk tube
2. 2
   أخرىequipped with a rubber septum
3. 3
   درجة الحرارةwas cooled under an argon
4. 4
   أخرىpurge
5. 5
   أخرىThe septum was removed
6. 6
   أخرىThe tube was capped with the septum
7. 7
   أخرىpurged with argon, and additional toluene (4 mL)
8. 8
   workup.ADDITIONwas added through the septum
9. 9
   درجة الحرارةThe mixture was heated to 100° C.
10. 10
    workup.STIRRINGwith stirring until the starting ketone
11. 11
    أخرىhad been completely consumed
12. 12
    درجة الحرارةThe mixture was cooled to room temperature
13. 13
    أخرىquenched with saturated aqueous ammonium chloride (10 mL)
14. 14
    workup.ADDITIONdiluted with ether (20 mL)
15. 15
    workup.ADDITIONThe mixture was poured into a separatory funnel
16. 16
    أخرىthe layers were separated
17. 17
    استخلاصThe aqueous layer was extracted with ether (20 mL)
18. 18
    غسيلthe combined organic layers were washed with brine (20 mL)
19. 19
    تجفيفdried over anhydrous magnesium sulfate
20. 20
    ترشيحfiltered
21. 21
    تركيزconcentrated in vacuo
22. 22
    أخرىThe crude material was purified by flash chromatography on silica gel

الإجراء التجريبي

An oven dried Schlenk tube equipped with a rubber septum was cooled under an argon purge. The septum was removed and the tube was charged with palladium acetate (5.6 mg, 0.025 mmol, 5 mol % Pd), (−)-2-(dicyclohexylphosphino)-2′-(dimethylamino)-1,1′-binaphthyl (10.5 mg, 0.038 mmol, 7.5 mol %) and 2-methyl-5-(N-methyl-anilinomethylene)cyclopentanone (108 mg, 0.5 mmol). Toluene (2 mL) was added and the mixture was stirred for 1 min at room temperature. 4-Bromobenzonitrile (182 mg, 1.0 mmol) and sodium t-butoxide (96 mg, 1.0 mmol) were added to the tube. The tube was capped with the septum, purged with argon, and additional toluene (4 mL) was added through the septum. The mixture was heated to 100° C. with stirring until the starting ketone had been completely consumed as judged by GC analysis. The mixture was cooled to room temperature, quenched with saturated aqueous ammonium chloride (10 mL) and diluted with ether (20 mL). The mixture was poured into a separatory funnel and the layers were separated. The aqueous layer was extracted with ether (20 mL), and the combined organic layers were washed with brine (20 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The crude material was purified by flash chromatography on silica gel to afford 80 mg (51%) of the title compound. The ee was determined to be 80% by chiral HPLC analysis.

المصدر