Sodium Bicarbonate → (2S)-5-(tert-butoxy)-2-{[(tert-butoxy)carbonyl]amino}-5-oxopentanoic acid

HRID 1532933ノート

反応式

HRID 1532933 の反応式
[NH2:1][C@H:2]([C:12]([OH:14])=[O:13])[CH2:3][CH2:4][C:5](=[O:11])[O:6][C:7]([CH3:10])([CH3:9])[CH3:8].[C:15]([O-:18])(O)=[O:16].[Na+]>O.O1CCOCC1>[NH:1]([C:15]([O:18][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:16])[C@H:2]([C:12]([OH:14])=[O:13])[CH2:3][CH2:4][C:5](=[O:11])[O:6][C:7]([CH3:10])([CH3:8])[CH3:9]

参加物

5

反応物 2

HCID 516892Sodium BicarbonateHCID 7010573(2S)-2-amino-5-(tert-butoxy)-5-oxopentanoic acid

生成物 1

HCID 6993432(2S)-5-(tert-butoxy)-2-{[(tert-butoxy)carbonyl]amino}-5-oxopentanoic acid

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

実験手順

H-Glu(OtBu)-OH (Rf(BuOH/AcOH/H2O 4:1:1 v/v/v): 0.52, [α]D=+9.3° C.=1.05 H2O, mp: 181° C. (dec.); lit24: [α]D=+9.8° C.=2 H2O, mp: 182° C.) (2.0 g, 9.85 mmol), NaHCO3 (1.86 g, 22.2 mmol, 2.25 eq.) were dissolved in H2O (40 mL) and Boc2O25 (2.36 g, 10.8 mmol, 1.10 eq.) dissolved in dioxane (20 mL) was added. The reaction mixture became turbid and gas evolution started. After 3 hrs of stirring at room temperature, the reaction mixture was partially evaporated in vacuo. The aqueous solution was acidified with 10% citric acid and the precipitating oil was taken up into EtOAc (three extractions 20 mL). The EtOAc layer was subsequently washed with H2O (five times 30 mL), saturated NaCl (three times 30 mL) and dried on Na2SO4. The residue obtained after evaporation in vacuo was an oil which crystallized slowly. Yield: 2.91 g (98%), Rf(BuOH/AcOH/H2O 4:1:1 v/v/v): 0.87, Rf(CH2Cl2/MeOH 9:1 v/v): 0.17, [α]D=−10.3° C.=0.93 MeOH, mp: 98-99° C. (lit26: [α]D=−10.9° C.=1 MeOH, mp:101-102° C.), 1H NMR (CDCl3): δ=1.44 (s, 18H, Boc/OtBu (2×9H)); 1.99/2.18 (dm, 2H, β-CH2); 2.38 (m, 2H, γ-CH2); 4.34 (m, 1H, α-CH); 5.23 (d, 1H, NH).

後処理

  1. additionwas added
  2. customthe reaction mixture was partially evaporated in vacuo
  3. washThe EtOAc layer was subsequently washed with H2O (five times 30 mL), saturated NaCl (three times 30 mL)
  4. customdried on Na2SO4
  5. customThe residue obtained
  6. customafter evaporation in vacuo
  7. customcrystallized slowly

出典と根拠

ORDレコード
ord-036ab89d60e7495ba9afb496dc2aa7ae
出典データセット
uspto-grants-2001_03
特許番号
US06207399B1

反応ノート

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