Thionyl Chloride → (S)-Methyl 2-((tert-butoxycarbonyl)amino)pent-4-ynoate

HRID 2264814ノート

反応式

HRID 2264814 の反応式
S(Cl)(Cl)=O.[NH2:5][C@@H:6]([CH2:10][C:11]#[CH:12])[C:7]([OH:9])=[O:8].[O:13](C(OC(C)(C)C)=O)[C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=O.[C:28]([O-])(O)=O.[Na+]>CO.C(OCC)(=O)C>[CH3:18][C:17]([O:16][C:14]([NH:5][C@@H:6]([CH2:10][C:11]#[CH:12])[C:7]([O:9][CH3:28])=[O:8])=[O:13])([CH3:20])[CH3:19]

参加物

7

反応物 4

HCID 24386Thionyl ChlorideHCID 90495Di-tert-butyl dicarbonateHCID 168091L-PropargylglycineHCID 516892Sodium Bicarbonate

生成物 1

HCID 11817013(S)-Methyl 2-((tert-butoxycarbonyl)amino)pent-4-ynoate収率 73%

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 8857Ethyl Acetate溶媒

実験手順

Thionylchloride (16 ml, 26 g, 221 mmol) was added dropwise to a cooled (0° C.) solution of (2S)-2-amino-4-pentynoic acid (5.0 g, 44.18 mmol, commercially) in methanol (dry, 100 ml). After stirring the mixture at room temperature for 5.5 hrs the solvent was evaporated and the residue was taken up in 1,4-dioxane (100 ml) and aqueous saturated NaHCO3 solution (50 ml). Then BOC2O (10.1 g, 46.4 mmol) was added and the mixture was stirred overnight at room temperature. Ethyl acetate and aqueous NaHCO3 solution were added. The separated organic layer was washed with bicarbonate solution, dried (Na2SO4), filtrated and evaporated. The resulting crude material was purified by chromatography on silica gel using ethyl acetate/cyclohexanes (1:100 to 3:7) to afford the title compound (7.35 g, 73%); MS: (ES/+) m/z: 250 [MNa]+, C11H17NO4 requires 227. 1H-NMR (400 MHz, DMSO-d6) δ (ppm): 7.3 (d, 1H), 4.1 (m, 1H), 2.9 (s, 1H), 2.6-2.5 (m, 2H), 1.4 (s, 9H).

後処理

  1. customwas evaporated
  2. stirringthe mixture was stirred overnight at room temperature
  3. washThe separated organic layer was washed with bicarbonate solution
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltrated
  6. customevaporated
  7. customThe resulting crude material was purified by chromatography on silica gel

出典と根拠

ORDレコード
ord-cbdd73e2589a4893ad2bafe84d604545
出典データセット
uspto-grants-2010_12
特許番号
US07855218B2

反応ノート

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