反応 #77846

反応方程式

tert-butyl 3-(5-bromopyridin-2-yl)prop-2-ynylcarbamate

N-Cbz propargylamine

→

6-1

収率 55.1%

Benzyl 3-(6-{3-[(tert-butoxycarbonyl)amino]prop-1-ynyl}pyridin-3-yl)prop-2-ynylcarbamate

収率 55.1%

溶媒

diisopropylamine

ethyl acetate

反応条件

後処理

1. 1
   温度was heated
2. 2
   温度under reflux under a nitrogen atmosphere for 3 hours
3. 3
   ろ過The precipitates were filtered
4. 4
   洗浄rinsed with ethyl acetate (30 mL)
5. 5
   濃縮concentrated under reduced pressure
6. 6
   その他purified by silica gel column chromatography
7. 7
   workup.ADDITIONa mixture of MTBE and hexanes (2:3 to 4:1)
8. 8
   workup.ADDITIONThe fractions containing the product
9. 9
   濃縮concentrated under reduced pressure
10. 10
    その他The residue was crystallized from MTBE
11. 11
    ろ過Crystals were filtered
12. 12
    洗浄washed with MTBE
13. 13
    その他dried

実験手順

A mixture of tert-butyl 3-(5-bromopyridin-2-yl)prop-2-ynylcarbamate (3-1) (1.44 g), N-Cbz propargylamine (1.09 g), Pd(PPh3)2Cl2 (73 mg), and CuI (10 mg) in diisopropylamine (25 mL) was heated under reflux under a nitrogen atmosphere for 3 hours. The mixture was cooled to ambient temperature and diluted with ethyl acetate (70 mL). The precipitates were filtered and rinsed with ethyl acetate (30 mL). The filtrate and washings were combined, concentrated under reduced pressure, and purified by silica gel column chromatography using a mixture of MTBE and hexanes (2:3 to 4:1). The fractions containing the product were combined and concentrated under reduced pressure. The residue was crystallized from MTBE. Crystals were filtered, washed with MTBE, and dried to give 6-1 (1.07 g). An additional 120 mg of 6-1 was isolated from the mother liquors and washings.

出典