Reacción #1563919

Ecuación de reacción

carbon monoxide

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

CH3CN

triethylamine

→

title compound

Rendimiento 143.2%

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

Rendimiento 143.2%

Disolventes

CH3OH

Condiciones de reacción

Tratamiento posterior

1. 1
   OtroSeal the vessel
2. 2
   Otrotransfer to a round-bottomed flask
3. 3
   Lavadorinsing with CH3OH
4. 4
   ConcentraciónConcentrate the mixture under reduced pressure
5. 5
   Otroto furnish an orange residue
6. 6
   ExtracciónAdd water (50 mL), then extract with EtOAc (2×50 mL)
7. 7
   LavadoWash the combined organic phases with saturated aqueous NaCl (25 mL)
8. 8
   Otroseparate the layers
9. 9
   Secadodry the organic phase over MgSO4
10. 10
    Filtraciónfilter
11. 11
    Otroto remove the solids
12. 12
    Concentraciónconcentrate the filtrate under reduced pressure
13. 13
    Otroto give crude product
14. 14
    OtroPurify the product by flash chromatography on silica gel eluting with a gradient of 0% to 60% EtOAc/hexanes
15. 15
    ConcentraciónConcentrate the fractions
16. 16
    workup.ADDITIONcontaining the desired product under reduced pressure

Procedimiento

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).

Fuente