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

HRID 451802ノート

反応式

HRID 451802 の反応式
[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

参加物

6

反応物 3

HCID 4311764Sodium borohydride2 回HCID 59201561HCID 59201561、化合物HCID 59201713HCID 59201713、化合物

生成物 2

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

試薬・触媒・溶媒 1

HCID 887Methanol溶媒2 回

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-4ab17a4660de47e1916bf15986aacd5f
出典データセット
uspto-grants-2013_07
特許番号
US08487108B2

反応ノート

読み込み中…