(S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(2-(methoxy(methyl)amino)-2-oxoethyl)carbamate → (S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(3-methyl-2-oxobut-3-enyl)carbamate

HRID 627072Notes

Reaction equation

HRID 627072 reaction equation
[Si:1]([O:8][CH2:9][C@@H:10]([N:13]([CH2:21][C:22](N(OC)C)=[O:23])[C:14](=[O:20])[O:15][C:16]([CH3:19])([CH3:18])[CH3:17])[CH:11]=[CH2:12])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH2:28]=[C:29]([Mg]Br)[CH3:30]>C1COCC1>[Si:1]([O:8][CH2:9][C@@H:10]([N:13]([CH2:21][C:22](=[O:23])[C:29]([CH3:30])=[CH2:28])[C:14](=[O:20])[O:15][C:16]([CH3:18])([CH3:19])[CH3:17])[CH:11]=[CH2:12])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

4

Reactant 2

HCID 89855339(S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(2-(methoxy(methyl)amino)-2-oxoethyl)carbamate2×HCID 178456138HCID 178456138, compound

Product 1

HCID 131735276(S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(3-methyl-2-oxobut-3-enyl)carbamateYield 89.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (S)-tert-butyl 1-(tert-butyldimethylsilyloxy)but-3-en-2-yl(2-(methoxy(methyl)amino)-2-oxoethyl)carbamate (Intermediate 5, 30.79 g, 76.48 mmol) in THF (200 mL) at 0° C. was added prop-1-en-2-ylmagnesium bromide (0.5M in THF) (300 mL, 149.90 mmol). The reaction mixture was stirred at 0° C. for 1 hour. The reaction mixture was quenched with 200 mL 10% citric acid, diluted further with 100 mL water and extracted with ether. The organics were concentrated and the resulting oil was dissolved in ether and washed with water and brine. The organics were dried over magnesium sulfate, filtered and concentrated. Silica gel chromatography (0%-20% ethyl acetate/hexanes) afforded the desired product (26.2 g, 89%) as a colorless oil.

Workup

  1. customThe reaction mixture was quenched with 200 mL 10% citric acid
  2. additiondiluted further with 100 mL water
  3. extractionextracted with ether
  4. concentrationThe organics were concentrated
  5. dissolutionthe resulting oil was dissolved in ether
  6. washwashed with water and brine
  7. dry with materialThe organics were dried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-89d08311e8c24e889399f4896d0535bd
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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