Acetic Acid → N-(t-Butoxycarbonyl)-alpha-(4-hydroxy-2,3,5,6-tetrahydro-4-pyranyl)glycine, benzyl ester

HRID 2118843ノート

反応式

HRID 2118843 の反応式
C(NC(C)C)(C)C.C([Li])CCC.[C:13]([O:17][C:18]([NH:20][CH2:21][C:22]([O:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)=[O:23])=[O:19])([CH3:16])([CH3:15])[CH3:14].[O:32]1[CH2:37][CH2:36][C:35](=[O:38])[CH2:34][CH2:33]1.C(O)(=O)C>O1CCCC1.CCCCCC.O>[C:13]([O:17][C:18]([NH:20][CH:21]([C:35]1([OH:38])[CH2:36][CH2:37][O:32][CH2:33][CH2:34]1)[C:22]([O:24][CH2:25][C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1)=[O:23])=[O:19])([CH3:16])([CH3:14])[CH3:15]

参加物

9

反応物 5

HCID 176Acetic AcidHCID 7912DiisopropylamineHCID 121599Tetrahydro-4H-pyran-4-oneHCID 357720Benzyl 2-(((tert-butoxy)carbonyl)amino)acetateHCID 178418339Butyllithium

生成物 1

HCID 13754449N-(t-Butoxycarbonyl)-alpha-(4-hydroxy-2,3,5,6-tetrahydro-4-pyranyl)glycine, benzyl ester

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒4 回HCID 8058Hexane溶媒

反応条件

温度
-72 °C

実験手順

A solution of diisopropylamine (17.5 ml, 0.127 moles) in 300 ml of dry tetrahydrofuran at -45° C. under argon was treated with 70 ml (0.117 moles) of 1.71M n-butyllithium (in hexane). After 20 minutes at -45° C., the mixture was cooled to -72° C. and treated with 13.3 g (0.05 moles) of dried N-(t-butoxycarbonyl)glycine, benzyl ester in 60 ml of dry tetrahydrofuran. After 50 minutes, the dark yellow homogeneous solution was treated with 5 ml (5.43 g, 0.0543 moles) of tetrahydro-4-pyranone in 50 ml of tetrahydrofuran and the temperature allowed to rise to 0° C. over 1.5 hours. A solution of 7.2 g (0.12 moles) of glacial acetic acid in 20 ml of tetrahydrofuran was added to the purple solution, and the resulting light yellow turbid mixture was poured into 1L of water and extracted with ethyl acetate. The organic layer was washed with 2% potassium bisulfate, 5% sodium bicarbonate and brine, dried (sodium sulfate) and evaporated to an oil. Chromatography on 800 ml of LPS-1 in hexane:ethyl acetate (1:1) and combination of the product fractions (Rf=0.32 in the same solvent) gave an oil which solidified on trituration with hexane yielding a total of 10.34 g of product as a white solid, melting point 90°-93° C.

後処理

  1. waitAfter 50 minutes
  2. waitto rise to 0° C. over 1.5 hours
  3. extractionextracted with ethyl acetate
  4. washThe organic layer was washed with 2% potassium bisulfate, 5% sodium bicarbonate and brine
  5. dry with materialdried (sodium sulfate)
  6. customevaporated to an oil
  7. customChromatography on 800 ml of LPS-1 in hexane:ethyl acetate (1:1) and combination of the product fractions (Rf=0.32 in the same solvent) gave an oil which

出典と根拠

ORDレコード
ord-0162138d7bbe4596a2f6ade276ad4fe0
出典データセット
uspto-grants-1987_07
特許番号
US04680388

反応ノート

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