2-Bromopyridine → HCID 22843545、化合物

HRID 1030525ノート

反応式

HRID 1030525 の反応式
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.C([Li])CCC.[C:13]([O:17][C:18]([NH:20][C@H:21]([CH:26]=[O:27])[CH2:22][CH:23]([CH3:25])[CH3:24])=[O:19])([CH3:16])([CH3:15])[CH3:14]>O1CCCC1>[C:13]([O:17][C:18]([NH:20][CH:21]([CH2:22][CH:23]([CH3:25])[CH3:24])[C@H:26]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1)[OH:27])=[O:19])([CH3:16])([CH3:15])[CH3:14]

参加物

5

反応物 3

HCID 79732-BromopyridineHCID 104275tert-butyl N-[(2S)-4-methyl-1-oxopentan-2-yl]carbamateHCID 178418339Butyllithium

生成物 1

HCID 22843545HCID 22843545、化合物収率 21.6%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

実験手順

To 2-bromopyridine (3.16 g) in 20 ml of dry tetrahydrofuran cooled to -78° C. under argon was added slowly 11.2 ml of n-butyl lithium in tetrahydrofuran (2M). The solution was stirred for 5 minutes and then 2.1 g of N-t-butoxycarbonyl-L-leucinal in 10 ml of tetrahydrofuran was added. The mixture was stirred for 35 minutes, then quenched with 10 ml of saturated sodium sulfate solution, warmed to room temperature and poured into 50 ml of water. The mixture was extracted with ethyl acetate. The extract was dried (Na2SO4) and the solvent removed under vacuum. The residue was chromatographed over silica gel with ethyl acetatheexane (3:7) as eluent and then ethyl acetate-hexane (1:1) as eluent to give 0.62 g of (S) 2-tert-butoxycarbonyl-amino-4-methyl(R,S)1-(2-pyridinyl)pentan-1-ol as a yellow oil; [α]D26 -21°±3° (C, 0.329, dichloromethane). A4.12 sample of the preceding compound in a mixture of 15 ml of dichloromethane and 5 ml of acetic anhydride was stirred at room temperature for 22 hours. The mixture was concentrated under vacuum. The residue was dissolved in dichloromethane and the solution washed with saturated agneous sodium carbonate, dried (Na2SO4) and the solvent removed. The residue was chromatographed over silica gel with 30% ethyl acetate in hexane to give 1.55 g of (S) 2-tert-butoxycarbonylamino-4-methyl-(S)1-(2-pyridinyl)pentan-1-ol, 0-acetate as crystals, mp 83°-84° C.; [α]D26 -62°±1° (C. 1.01, dichloromethane) and (S) 2-tert-butoxycarbonylamino-4-methyl-(R)1-(2-pyridinyl)pentan-1-ol, 0-acetate as an amber oil; [α]D26 +3°±1° (C, 1.-66, methanol).

後処理

  1. stirringThe mixture was stirred for 35 minutes
  2. customquenched with 10 ml of saturated sodium sulfate solution
  3. additionpoured into 50 ml of water
  4. extractionThe mixture was extracted with ethyl acetate
  5. dry with materialThe extract was dried (Na2SO4)
  6. customthe solvent removed under vacuum
  7. customThe residue was chromatographed over silica gel with ethyl acetatheexane (3:7) as eluent

出典と根拠

ORDレコード
ord-80a6292dc07744229e9e65d62f496a33
出典データセット
uspto-grants-1992_04
特許番号
US05106835

反応ノート

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