Piperidine → 3-Amino-1-(tert-butoxycarbonyl)piperidine-3-carboxylic acid

HRID 1867753ノート

反応式

HRID 1867753 の反応式
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH2:11][C:10]([NH:17]C(OCC2C3C=CC=CC=3C3C2=CC=CC=3)=O)([C:14]([OH:16])=[O:15])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(OC)(C)(C)C.C(O)(C)C.N1CCCCC1>CN(C)C=O>[NH2:17][C:10]1([C:14]([OH:16])=[O:15])[CH2:11][CH2:12][CH2:13][N:8]([C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:7])[CH2:9]1

参加物

5

反応物 3

HCID 8082PiperidineHCID 27344081-((tert-butoxy)carbonyl)-3-(((9H-fluoren-9-ylmethoxy)carbonyl)amino)piperidine-3-carboxylic acid2 回HCID 86616950TBME isopropanol

生成物 1

HCID 247296423-Amino-1-(tert-butoxycarbonyl)piperidine-3-carboxylic acid収率 81%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

1-(tert-butoxycarbonyl)-3-{[(9H-fluoren-9-ylmethoxy)carbonyl]amino}piperidine-3-carboxylic acid was resolved by chiral HPLC resolution {Merck 50 mm 16 μm Kromasil Chirose 2 No. CT9014, tert-butylmethylether/iso-propanol (90/10). The first eluted enantiomer (800 mg, 1.71 mmol) 1-(tert-butoxycarbonyl)-3-{[(9H-fluoren-9-ylmethoxy)carbonyl]amino}piperidine-3-carboxylic acid (Isomer 1) was dissolved in N,N-dimethylformamide (10 ml) and piperidine (0.85 ml, 8.55 mmol) added. The mixture was stirred at room temperature over night. The resulting white precipitate was filtered off. The filtrates were concentrated and the residues purified by column chromatography on silica eluting with saturated ammonia in methanol/dichloromethane (25/75). The fractions containing the desired product were combined with the filtered solids and evaporated to give 3-amino-1-(tert-butoxycarbonyl)piperidine-3-carboxylic acid (Isomer 1) (339 mg, 81%); 1H NMR Spectrum: (D2O) 1.44 (s, 9H); 1.63 (m, 1H); 1.79 (d, 1H); 1.97 (d, 1H); 2.10 (m, 1H); 2.88 (t, 1H); 3.33 (d, 1H); 4.09 (m, 2H).

後処理

  1. filtrationThe resulting white precipitate was filtered off
  2. concentrationThe filtrates were concentrated
  3. customthe residues purified by column chromatography on silica eluting with saturated ammonia in methanol/dichloromethane (25/75)
  4. additionThe fractions containing the desired product
  5. customevaporated

出典と根拠

ORDレコード
ord-fd232c69c90944ada391054ec49e10f5
出典データセット
uspto-grants-2009_12
特許番号
US07632840B2

反応ノート

読み込み中…