تفاعل #1563919

معادلة التفاعل

carbon monoxide

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

CH3CN

triethylamine

→

title compound

المردود 143.2%

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

المردود 143.2%

المذيبات

CH3OH

ظروف التفاعل

المعالجة

1. 1
   أخرىSeal the vessel
2. 2
   أخرىtransfer to a round-bottomed flask
3. 3
   غسيلrinsing with CH3OH
4. 4
   تركيزConcentrate the mixture under reduced pressure
5. 5
   أخرىto furnish an orange residue
6. 6
   استخلاصAdd water (50 mL), then extract with EtOAc (2×50 mL)
7. 7
   غسيلWash the combined organic phases with saturated aqueous NaCl (25 mL)
8. 8
   أخرىseparate the layers
9. 9
   تجفيفdry the organic phase over MgSO4
10. 10
    ترشيحfilter
11. 11
    أخرىto remove the solids
12. 12
    تركيزconcentrate the filtrate under reduced pressure
13. 13
    أخرىto give crude product
14. 14
    أخرىPurify the product by flash chromatography on silica gel eluting with a gradient of 0% to 60% EtOAc/hexanes
15. 15
    تركيزConcentrate the fractions
16. 16
    workup.ADDITIONcontaining the desired product under reduced pressure

الإجراء التجريبي

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).

المصدر