반응 #1962483

반응 방정식

6-iodo-hex-1-yne

L-alanine methyl ester hydrochloride

K2CO3

N2

→

N-(5-hexynyl) L-alanine methyl ester

수율 56.0%

용매

tetrahydrofuran

반응 조건

후처리

1. 1
   workup.STIRRINGwas stirred
2. 2
   온도The reaction mixture was refluxed at ˜70° C. for 15-18 h with TLC check
3. 3
   기타After consumption of the starting material
4. 4
   온도the mixture was cooled to room temperature
5. 5
   workup.ADDITIONdiluted by diethylether
6. 6
   여과filtered
7. 7
   workup.ADDITIONThe filtrate was further diluted by diethylether
8. 8
   여과filtered again
9. 9
   기타The solvent was removed by rotavap
10. 10
    기타the crude product was purified by flash chromatography on silica gel (1:2=Hexane/EtOAc, 1% triethylamine)

실험 절차

In a flame-baked, two neck 100 mL round bottom flask, 20 mmol of L-alanine methyl ester hydrochloride (2.8 g), 40 mmol of K2CO3 (5.53 g), and 20 mmol of tetrabutylammonium iodide (TBAI, 7.39 g) were charged under a stream of dry N2 gas. 35 mL of tetrahydrofuran (THF) was slowly added and the mixture was stirred for 15 min at room temperature. 2.6 mL of 6-iodo-hex-1-yne was added dropwise while the mixture was stirred. The reaction mixture was refluxed at ˜70° C. for 15-18 h with TLC check. After consumption of the starting material, the mixture was cooled to room temperature, diluted by diethylether, and filtered. The filtrate was further diluted by diethylether and filtered again. The solvent was removed by rotavap and the crude product was purified by flash chromatography on silica gel (1:2=Hexane/EtOAc, 1% triethylamine) to give N-(5-hexynyl) L-alanine methyl ester (2.044 g, 11.2 mmol) as a yellow oil. Yield: 56%. Rf=0.27 (1:1=Hexane/EtOAc); ESI-MS [M+H]+=184.1 m/z; 1H NMR (300 MHz, CDCl3): δ 3.70 (s, 3H), 3.32 (q, J=7.0 Hz, 1H), 2.53 (m, 2H), 2.18 (m, 2H), 1.92 (t, J=2.6 Hz, 1H), 1.56 (m, 5H), 1.27 (d, J=7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3): δ 176.29, 84.21, 68.41, 56.61, 51.74, 47.41, 29.20, 26.01, 19.11, 18.23.

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