N,N,N',N'-Tetramethylethylenediamine → HCID 69472852, compound

HRID 1600845Notes

Reaction equation

HRID 1600845 reaction equation
[CH3:1][O:2][C:3](=[O:16])[CH2:4][NH:5][C:6]([O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:7].C(NC(C)C)(C)C.[Li].CN(C)CCN(C)C.I[CH2:34][Si:35]([CH3:38])([CH3:37])[CH3:36]>C1COCC1.CN(C)P(N(C)C)(N(C)C)=O>[CH2:9]([O:8][C:6]([NH:5][CH:4]([CH2:34][Si:35]([CH3:38])([CH3:37])[CH3:36])[C:3]([O:2][CH3:1])=[O:16])=[O:7])[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

7

Reactant 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 71033Methyl N-benzyloxycarbonylglycinateHCID 77877(Iodomethyl)trimethylsilaneHCID 45051747Lithium diisopropylamine

Product 1

HCID 69472852HCID 69472852, compoundYield 56%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of 5.58 g (25 mmol) of N-benzyloxycarbonyl glycine methyl ester in dry THF (70 ml) is added dropwise to a solution at -78° C. of lithium diisopropylamine (8.76 ml, 62.5 mmol) and tetramethylethylene diamine (9.43 ml, 62.5 mmol) in dry THF (100 ml), under nitrogen. After the addition is complete, the solution is stirred for 2 hours at -78° C., then 15 minutes at -30° C. and cooled to -78° C. A solution of 5.36 g (25 mmol) of iodomethyl-trimethylsilane in dry hexamethylphosphoramide (39 ml) is added dropwise to the resultant syrupy mixture. After the addition is complete, the reaction mixture is warmed up to -50° C., kept at this temperature for 1 hour and cooled to -78° C., just before hydrolysis. The reaction mixture is quenched by addition of water and ammonium chloride and diluted with ether. The organic layer is washed with 1N potassium hydrogen sulfate, twice with water and dried over sodium sulfate. The solvent is evaporated and the residue obtained (8.03 g) is purified by flash chromatography (silica gel,ethyl acetate/petroleum ether: 2/8). 4.30 g of the title compound are obtained (yield: 56%) (colorless oil). Rf : 0.51 (ethyl acetate/petroleum ether: 2/8).

Workup

  1. additionAfter the addition
  2. temperature15 minutes at -30° C. and cooled to -78° C
  3. additionAfter the addition
  4. temperaturethe reaction mixture is warmed up to -50° C.
  5. waitkept at this temperature for 1 hour
  6. temperaturecooled to -78° C., just before hydrolysis
  7. customThe reaction mixture is quenched by addition of water and ammonium chloride
  8. additiondiluted with ether
  9. washThe organic layer is washed with 1N potassium hydrogen sulfate, twice with water
  10. dry with materialdried over sodium sulfate
  11. customThe solvent is evaporated
  12. customthe residue obtained (8.03 g)
  13. customis purified by flash chromatography (silica gel,ethyl acetate/petroleum ether: 2/8)

Sources & evidence

ORD record
ord-49bf111edbaa42ebb320c7c46e88f4c0
Source dataset
uspto-grants-1999_11
Patent number
US05977074

Reaction notes

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