Benzaldehyde → NepsilonBenzyl-Nalpha-BOC-L-Lysine tert-Butyl Ester

HRID 1068070노트

반응식

HRID 1068070 반응식
Cl.[C:2]([O:6][C:7](=[O:22])[C@H:8]([CH2:17][CH2:18][CH2:19][CH2:20][NH2:21])[NH:9][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])([CH3:5])([CH3:4])[CH3:3].[CH:23](=O)[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.CCO.C([BH3-])#N.[Na+]>C(Cl)(Cl)Cl>[C:2]([O:6][C:7](=[O:22])[C@H:8]([CH2:17][CH2:18][CH2:19][CH2:20][NH:21][CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[NH:9][C:10]([O:12][C:13]([CH3:14])([CH3:15])[CH3:16])=[O:11])([CH3:5])([CH3:3])[CH3:4]

참가 물질

6

반응물 4

HCID 240BenzaldehydeHCID 702EthanolHCID 5003444Sodium cyanoborohydrideHCID 51358437(S)-tert-Butyl 6-amino-2-((tert-butoxycarbonyl)amino)hexanoate hydrochloride

생성물 1

HCID 10786720NepsilonBenzyl-Nalpha-BOC-L-Lysine tert-Butyl Ester수율 54%

시약·촉매·용매 1

HCID 6212Chloroform용매

실험 절차

Nα-BOC-L-lysine t-butyl ester hydrochloride salt (3) (25.97 g, 76.64 mmol) was dissolved in CHCl3 (300 ml) and washed with saturated aqueous Na2CO3 solution (2×100 ml). The organic layer was separated, dried (MgSO4), filtered and concentrated. The resultant oil (the free amine) was combined with benzaldehyde (10.42 g, 98.13 mmol), EtOH (150 ml) and activated 3 Å molecular sieves (46.0 g). The mixture was stirred under N2 for 6 hours. Sodium cyanoborohydride (2.41 g, 38.4 mmol) was added, and the mixture was stirred overnight at room temperature. The brown mixture was filtered, and the filtrate was acidified to pH 2 with 1 N HCl (110 ml). The yellow solution was concentrated to dryness, dissolved in CHCl3, and washed with saturated Na2CO3 solution and water. The organic layer was separated, dried (MgSO4) and concentrated. Flash column chromatography (10% EtOH/CHCl3, Rf=0.30) afforded the Nε-benzyl-Nα-BOC-L-lysine t-butyl ester (4) (16.16 g, 54%) as a colorless oil. 1H NMR (CD3OD) δ 7.34-7.20 (m, 5H), 3.91 (dd, 1H, J=9.0, 5.1), 3.72 (s, 2H), 2.58 (t, 2H, J=7.2), 1.82-1.30 (m, 6H), 1.45 (s, 9H), 1.43 (s, 9H); 13C NMR (CDCl3) δ 171.9, 155.3, 140.1, 128.3, 128.1, 126.9, 81.6, 79.5, 53.9, 48.9, 32.7, 29.5, 28.3, 27.9, 22.9. HRMS m/z calcd. for C22H36N2O4 392.2675, found 392.2676. Anal. calcd. for C22H36N2O4: C 67.32, H 9.24, N 7.14. Found: C 67.40, H 9.28, N 7.16. [α]25D=6.9° (c =1.00, CHCl3).

후처리

  1. washwashed with saturated aqueous Na2CO3 solution (2×100 ml)
  2. customThe organic layer was separated
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. stirringthe mixture was stirred overnight at room temperature
  7. filtrationThe brown mixture was filtered
  8. concentrationThe yellow solution was concentrated to dryness
  9. dissolutiondissolved in CHCl3
  10. washwashed with saturated Na2CO3 solution and water
  11. customThe organic layer was separated
  12. dry with materialdried (MgSO4)
  13. concentrationconcentrated

출처 및 근거

ORD 기록
ord-1166ac7d23c44a279a875740b769475e
출처 데이터셋
uspto-grants-2001_06
특허 번호
US06248866B1

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