반응 #742298

ord-2a961c3ea08944c1b8444fde543c17cf

반응 방정식

[CH3][Al]([CH3])[CH3]
Trimethylaluminium
Cc1cnc(N)cn1
5-methylpyrazin-2-amine
O=C([O-])[C@H](O)[C@@H](O)C(=O)[O-].[K+].[Na+]
Rochelle salt
COC(=O)[C@@H](O)CN1CC(O[Si](C)(C)C(C)(C)C)C1
(S)-methyl 3-(3-(tert-butyldimethyl-silyloxy)azetidin-1-yl)-2-hydroxypropanoate
Cc1cnc(NC(=O)[C@@H](O)CN2CC(O[Si](C)(C)C(C)(C)C)C2)cn1
product
수율 59.2%
Cc1cnc(NC(=O)[C@@H](O)CN2CC(O[Si](C)(C)C(C)(C)C)C2)cn1
(S)-3-(3-(tert-butyldimethylsilyloxy)azetidin-1-yl)-2-hydroxy-N-(5-methylpyrazin-2-yl)propanamide
수율 59.2%

반응 조건

온도
0°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    온도to warm to room temperature
  2. 2
    온도heated at 80° C. overnight
  3. 3
    온도to cool to room temperature
  4. 4
    workup.STIRRINGto stir for 2 hours
  5. 5
    기타The organic layer was separated
  6. 6
    추출the aqueous was extracted with ethyl acetate (75 mL)
  7. 7
    세척The combined organics were washed with brine (75 mL)
  8. 8
    건조dried (MgSO4)
  9. 9
    여과filtered
  10. 10
    기타evaporated
  11. 11
    기타The crude product was purified by flash silica chromatography
  12. 12
    세척eluting with 20 to 50% ethyl acetate in isohexane
  13. 13
    기타This was further purified by flash silica chromatography
  14. 14
    세척eluting with 0 to 10% methanol in dichloromethane

실험 절차

Trimethylaluminium (6.22 mL, 12.44 mmol) was added to 5-methylpyrazin-2-amine (1.357 g, 12.44 mmol) in anhydrous toluene (20 mL) cooled to 0° C. under nitrogen. The resulting solution was stirred at 0° C. for 10 minutes. (S)-methyl 3-(3-(tert-butyldimethyl-silyloxy)azetidin-1-yl)-2-hydroxypropanoate (Intermediate AD3) (2 g, 6.91 mmol) in anhydrous toluene (10 mL) was added and the resulting solution was allowed to warm to room temperature and then heated at 80° C. overnight. The reaction was allowed to cool to room temperature and a solution of Rochelle salt in water (20%, 75 ml) was added. The mixture diluted with water (25 mL) and ethyl acetate (75 mL) and allowed to stir for 2 hours. The organic layer was separated and the aqueous was extracted with ethyl acetate (75 mL). The combined organics were washed with brine (75 mL), dried (MgSO4), filtered and evaporated. The crude product was purified by flash silica chromatography, eluting with 20 to 50% ethyl acetate in isohexane. This was further purified by flash silica chromatography, eluting with 0 to 10% methanol in dichloromethane, to afford the product (1.50 g, 59.2%). 1H NMR (400 MHz, CDCl3) δ 0.03 (3H, d), 0.04 (3H, s), 0.87 (9H, q), 2.54 (3H, s), 2.93 (2H, d), 3.09 (2H, q), 3.71-3.77 (2H, m), 4.04 (1H, t), 4.46 (1H, t), 8.13 (1H, d), 9.39 (1H, d), 9.81 (1H, s); m/z (ES+) (M+H)+=367.34; HPLC tR=1.76 min.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US08071585B2uspto-grants-2011_12