Sodium borohydride → (3R,4R)-benzyl 3-amino-4-(tosyloxy)piperidine-1-carboxylate

HRID 451802Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 451802
[BH4-].[Na+].[N:3]([C@@H:6]1[CH2:11][CH2:10][N:9]([C:12]([O:14][CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[O:13])[CH2:8][C@H:7]1[O:22][S:23]([C:26]1[CH:32]=[CH:31][C:29]([CH3:30])=[CH:28][CH:27]=1)(=[O:25])=[O:24])=[N+]=[N-].[N:33]([C@H:36]1[C@H:41]([O:42][S:43]([C:46]2[CH:52]=[CH:51][C:49]([CH3:50])=[CH:48][CH:47]=2)(=[O:45])=[O:44])[CH2:40][CH2:39][N:38]([C:53]([O:55][CH2:56][C:57]2[CH:62]=[CH:61][CH:60]=[CH:59][CH:58]=2)=[O:54])[CH2:37]1)=[N+]=[N-]>CO>[NH2:3][C@@H:6]1[CH2:11][CH2:10][N:9]([C:12]([O:14][CH2:15][C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)=[O:13])[CH2:8][C@H:7]1[O:22][S:23]([C:26]1[CH:27]=[CH:28][C:29]([CH3:30])=[CH:31][CH:32]=1)(=[O:25])=[O:24].[NH2:33][C@H:36]1[C@H:41]([O:42][S:43]([C:46]2[CH:47]=[CH:48][C:49]([CH3:50])=[CH:51][CH:52]=2)(=[O:44])=[O:45])[CH2:40][CH2:39][N:38]([C:53]([O:55][CH2:56][C:57]2[CH:58]=[CH:59][CH:60]=[CH:61][CH:62]=2)=[O:54])[CH2:37]1

Komponenten

6

Edukt 3

HCID 4311764Sodium borohydride2×HCID 59201561HCID 59201561, VerbindungHCID 59201713HCID 59201713, Verbindung

Produkt 2

HCID 59201302trans-Benzyl 4-amino-3-(tosyloxy)piperidine-1-carboxylateHCID 59201320(3R,4R)-benzyl 3-amino-4-(tosyloxy)piperidine-1-carboxylateAusbeute 64 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel2×

Versuchsvorschrift

To a 0° C. solution of CuSO4.5H2O (642 mg, 0.5 equiv) in methanol (30 mL), NaBH4 (200 mg, 1.05 equiv) was added. To the stirred black suspension was added a solution of trans-benzyl 4-azido-3-(tosyloxy)piperidine-1-carboxylate and trans-benzyl 3-azido-4-(tosyloxy)piperidine-1-carboxylate (2.21 g, 5.14 mmol) in methanol (20 mL). Additional NaBH4 (578 mg, 3 equiv) was added in four portions over the course of 1 h. The reaction mixture was filtered through a pad of Celite and concentrated. The residue was diluted with CH2Cl2 (70 mL), washed with water (15 mL), satd aq NH4Cl solution (2×10 mL), brine (15 mL), and dried over Na2SO4. Concentration afforded trans-benzyl 4-amino-3-(tosyloxy)piperidine-1-carboxylate and trans-benzyl 3-amino-4-(tosyloxy)piperidine-1-carboxylate (1.34 g, 64%). The product was used for the next step without further purification. MS ESI +ve m/z 405 (M+1).

Aufarbeitung

  1. filtrationThe reaction mixture was filtered through a pad of Celite
  2. concentrationconcentrated
  3. additionThe residue was diluted with CH2Cl2 (70 mL)
  4. washwashed with water (15 mL)
  5. dry with materialdried over Na2SO4
  6. concentrationConcentration

Quellen und Nachweise

ORD-Eintrag
ord-4ab17a4660de47e1916bf15986aacd5f
Quelldatensatz
uspto-grants-2013_07
Patentnummer
US08487108B2

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