Реакция #1563919

Уравнение реакции

carbon monoxide

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

CH3CN

triethylamine

→

title compound

Выход 143.2%

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

Выход 143.2%

Растворители

CH3OH

Условия реакции

Обработка

1. 1
   ДругоеSeal the vessel
2. 2
   Другоеtransfer to a round-bottomed flask
3. 3
   Промывкаrinsing with CH3OH
4. 4
   КонцентрированиеConcentrate the mixture under reduced pressure
5. 5
   Другоеto furnish an orange residue
6. 6
   ЭкстракцияAdd water (50 mL), then extract with EtOAc (2×50 mL)
7. 7
   ПромывкаWash the combined organic phases with saturated aqueous NaCl (25 mL)
8. 8
   Другоеseparate the layers
9. 9
   Сушкаdry the organic phase over MgSO4
10. 10
    Фильтрацияfilter
11. 11
    Другоеto remove the solids
12. 12
    Концентрированиеconcentrate the filtrate under reduced pressure
13. 13
    Другоеto give crude product
14. 14
    ДругоеPurify the product by flash chromatography on silica gel eluting with a gradient of 0% to 60% EtOAc/hexanes
15. 15
    КонцентрированиеConcentrate the fractions
16. 16
    workup.ADDITIONcontaining the desired product under reduced pressure

Методика

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).

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