反応 #1563919

反応方程式

carbon monoxide

(S)—N-tert-butoxycarbonyl-1-(4-bromophenyl)ethylamine

CH3CN

triethylamine

→

title compound

収率 143.2%

methyl (S)-4-(1-tert-butoxycarbonylaminoethyl)benzoate

収率 143.2%

溶媒

CH3OH

反応条件

後処理

1. 1
   その他Seal the vessel
2. 2
   その他transfer to a round-bottomed flask
3. 3
   洗浄rinsing with CH3OH
4. 4
   濃縮Concentrate the mixture under reduced pressure
5. 5
   その他to furnish an orange residue
6. 6
   抽出Add water (50 mL), then extract with EtOAc (2×50 mL)
7. 7
   洗浄Wash the combined organic phases with saturated aqueous NaCl (25 mL)
8. 8
   その他separate the layers
9. 9
   乾燥dry the organic phase over MgSO4
10. 10
    ろ過filter
11. 11
    その他to remove the solids
12. 12
    濃縮concentrate the filtrate under reduced pressure
13. 13
    その他to give crude product
14. 14
    その他Purify the product by flash chromatography on silica gel eluting with a gradient of 0% to 60% EtOAc/hexanes
15. 15
    濃縮Concentrate the fractions
16. 16
    workup.ADDITIONcontaining the desired product under reduced pressure

実験手順

To a Parr autoclave with mechanical stirring, add Pd(OAc)2 (120 mg, 0.53 mmol), 1,1′-bis(diphenylphosphino)ferrocene (355 mg, 0.64 mmol), (S)—N-tert-butoxycarbonyl-1-(4-bromophenyl)ethylamine (1.50 g, 5.0 mmol), anhydrous CH3CN (45 mL), anhydrous CH3OH (30 mL), and triethylamine (1.9 mL, 13.63 mmol). Seal the vessel and pressurize with carbon monoxide to 724 kPag. Heat the vessel to 85° C. and stir the mixture overnight. Vent the reaction vessel (Caution—poison gas!) and transfer to a round-bottomed flask, rinsing with CH3OH. Concentrate the mixture under reduced pressure to furnish an orange residue. Add water (50 mL), then extract with EtOAc (2×50 mL). Wash the combined organic phases with saturated aqueous NaCl (25 mL), then separate the layers, dry the organic phase over MgSO4, filter to remove the solids, and concentrate the filtrate under reduced pressure to give crude product. Purify the product by flash chromatography on silica gel eluting with a gradient of 0% to 60% EtOAc/hexanes. Concentrate the fractions containing the desired product under reduced pressure to furnish the title compound as a white solid (1.00 g, 72% yield). Mass spectrum (m/z) 224 (M+2H−t-Bu)+, 302 (M+Na)+, 581 (2M+Na)+. 1H NMR (400 MHz, DMSO-d6): δ 7.89 (d, =8.4 Hz, 2H), 7.41 (d, J=8.2 Hz, 2H), 4.64 (dq, J=7.4, 6.8 Hz, 1H), 3.82 (s, 3H), 1.34 (br s, 9H), 1.28 (d, J=7.2 Hz, 3H).

出典