Sodium Bicarbonate → (2R,4R)-4-Azido-2-hydroxymethyl-pyrrolidine-1-carboxylic acid tert-butyl ester

HRID 244349ノート

反応式

HRID 244349 の反応式
[BH4-].[Li+].C[O:4][C:5]([C@H:7]1[CH2:11][C@@H:10]([N:12]=[N+:13]=[N-:14])[CH2:9][N:8]1[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=O.C(=O)(O)[O-].[Na+]>CCOCC>[C:18]([O:17][C:15]([N:8]1[CH2:9][C@H:10]([N:12]=[N+:13]=[N-:14])[CH2:11][C@@H:7]1[CH2:5][OH:4])=[O:16])([CH3:21])([CH3:20])[CH3:19]

参加物

5

反応物 3

HCID 516892Sodium BicarbonateHCID 4148881Lithium borohydrideHCID 585644271-tert-butyl 2-methyl (2R,4R)-4-azidopyrrolidine-1,2-dicarboxylate

生成物 1

HCID 58564434(2R,4R)-4-Azido-2-hydroxymethyl-pyrrolidine-1-carboxylic acid tert-butyl ester収率 96.4%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

反応条件

温度
-70 °C

実験手順

Add lithium borohydride (8.50 g, 351 mmol) to a solution of (2R,4R)-4-azido-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester 2-methyl ester (95 g, 351 mmol) in ether (1 L) at −30° C. under nitrogen. Allow the temperature to rise to 0° C. over 1.5 h and stir for an additional 2 h. Cool to −70° C. and add saturated aqueous sodium bicarbonate (1 L) dropwise. Allow to warm to room temperature, separate the layers and extract the aqueous layer with ether (1 L). Combine the ether layers, dry over sodium sulfate, filter, and concentrate. Dry the resulting material under high vacuum to obtain a yellow oil (82 g, 96%). [α]D20+20.3 (c=1.0 in methanol). 1H NMR (400 MHz, DMSO-d6) δ 1.38 (s, 9H), 1.99 (br s, 1H, OH), 2.20 (m, 1H), 3.34 (m, 1H), 3.50-3.78 (m, 1H), 4.29 (m, 1H), 4.78 (m, 1H).

後処理

  1. temperatureto warm to room temperature
  2. customseparate the layers
  3. extractionextract the aqueous layer with ether (1 L)
  4. dry with materialCombine the ether layers, dry over sodium sulfate
  5. filtrationfilter
  6. concentrationconcentrate
  7. customDry the resulting material under high vacuum

出典と根拠

ORDレコード
ord-a166316af83d415ea0c7f72ca0c595a8
出典データセット
uspto-grants-2014_02
特許番号
US08658638B2

反応ノート

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