Pyridine → (R)-tert-butyl 1-cyanoethylcarbamate

HRID 77123

反応式

HRID 77123 の反応式
[NH2:1][C:2](=O)[C@H:3]([NH:5][C:6](=[O:12])[O:7][C:8]([CH3:11])([CH3:10])[CH3:9])[CH3:4].CC1C=CC(S(Cl)(=O)=O)=CC=1.N1C=CC=CC=1.C(OC(=O)C)(=O)C>C(Cl)Cl>[C:2]([C@H:3]([NH:5][C:6](=[O:12])[O:7][C:8]([CH3:11])([CH3:10])[CH3:9])[CH3:4])#[N:1]

参加物

6

反応物 4

HCID 1049PyridineHCID 73974-Toluenesulfonyl chlorideHCID 7918Acetic AnhydrideHCID 7015296Boc-D-Ala-NH2

生成物 1

HCID 5479028(R)-tert-butyl 1-cyanoethylcarbamate収率 37.2%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

To a solution of (R)-tert-butyl 1-amino-1-oxopropan-2-ylcarbamate (Int-X-A, 1 g, 5.31 mmol) and 4-methylbenzene-1-sulfonyl chloride (4.05 g, 21.25 mmol) in CH2Cl2 (5 mL) was added pyridine (2.101 g, 26.6 mmol). After 3 h, acetic anhydride (0.651 g, 6.38 mmol) was added. This was stirred overnight before it was concentrated and EtOAc was added. Saturated NaHCO3 was added and the two phase mixture was stirred vigorously for 2 h. The organic layer was washed with 1 N HCl and then saturated NaHCO3. The organic layer was dried and concentrated. The resulting residue was purified by flash chromatography (Isco Combiflash Companion, 40 g silica gel, 15% ethyl acetate-hexane) to provide the product (R)-tert-butyl 1-cyanoethylcarbamate (Int-X-B, 336 mg, 1.974 mmol, 37.2% yield); [M+Na]+=193.2; 1H NMR (400 MHz, methanol-d4) δ ppm 4.51 (1 H, q), 1.34-1.58 (12 H, m).

後処理

  1. concentrationwas concentrated
  2. additionEtOAc was added
  3. additionSaturated NaHCO3 was added
  4. stirringthe two phase mixture was stirred vigorously for 2 h
  5. washThe organic layer was washed with 1 N HCl
  6. customThe organic layer was dried
  7. concentrationconcentrated
  8. customThe resulting residue was purified by flash chromatography (Isco Combiflash Companion, 40 g silica gel, 15% ethyl acetate-hexane)

出典と根拠

ORDレコード
ord-e084edfba7704cc5bcdd40a16f9c1ce3
出典データセット
uspto-grants-2014_09
特許番号
US08835470B2

関連ノート

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