N,N,N',N'-Tetramethylethylenediamine → Methyl 3-((tert-butoxycarbonyl)amino)furan-2-carboxylate

HRID 881234

反応式

HRID 881234 の反応式
[O:1]1[CH:5]=[CH:4][C:3]([NH:6][C:7](=[O:13])[O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[CH:2]1.CN(CCN(C)C)C.C([Li])CCC.[C:27](=O)([O:30]C)[O:28][CH3:29]>C1COCC1>[CH3:29][O:28][C:27]([C:2]1[O:1][CH:5]=[CH:4][C:3]=1[NH:6][C:7](=[O:13])[O:8][C:9]([CH3:10])([CH3:12])[CH3:11])=[O:30]

参加物

6

反応物 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 12021Dimethyl CarbonateHCID 12207186tert-butyl N-(furan-3-yl)carbamateHCID 178418339Butyllithium

生成物 1

HCID 52987670Methyl 3-((tert-butoxycarbonyl)amino)furan-2-carboxylate収率 51%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

To a solution of tert-butyl furan-3-ylcarbamate 32 (1.7 g, 1.0 eq) in THF (50 ml) at −30° C. was added TMEDA (1.75 ml, 1.3 eq) followed by 1.6M solution of n-butyllithium (8.4 ml, 2.25 eq, 1.6M in hexanes). Reaction mixture was allowed to warm up to 0° C. and stirred for 1 h, before being cooled back to −30° C. Dimethyl carbonate (2.4 ml, 3.0 eq) was quickly added, before the reaction mixture was allowed to warm up to room temperature for 1 hr. Reaction mixture was quenched with 2M HCl, followed by addition of saturated aq. NaCl. Mixture was extracted with ethyl acetate. The combined organic extracts were dried with Na2SO4 and concentrated. The crude reaction mixture was purified by flash chromatography to yield tert-butyl 2-(methoxycarbonyl)furan-3-ylcarbamate 33 (1.14 g, 51%): MS (Q1) 242 (M)+.

後処理

  1. customReaction mixture
  2. temperaturebefore being cooled back to −30° C
  3. temperatureto warm up to room temperature for 1 hr
  4. customReaction mixture
  5. customwas quenched with 2M HCl
  6. additionfollowed by addition of saturated aq. NaCl
  7. extractionMixture was extracted with ethyl acetate
  8. dry with materialThe combined organic extracts were dried with Na2SO4
  9. concentrationconcentrated
  10. customThe crude reaction mixture
  11. customwas purified by flash chromatography

出典と根拠

ORDレコード
ord-8036493649f44dfabd0858bb3b92dbb3
出典データセット
uspto-grants-2015_03
特許番号
US08993563B2

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