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

HRID 881234

Reaction equation

HRID 881234 reaction equation
[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]

Participants

6

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

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)+.

Workup

  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

Sources & evidence

ORD record
ord-8036493649f44dfabd0858bb3b92dbb3
Source dataset
uspto-grants-2015_03
Patent number
US08993563B2

Linked notes

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