Allyl bromide → HCID 118342901, compound

HRID 2202709Notes

Reaction equation

HRID 2202709 reaction equation
[CH3:1][C:2]1([CH3:11])[N:6]2[C:7](=[O:10])[CH2:8][CH2:9][C@@H:5]2[CH2:4][O:3]1.[CH:12]([N-]C(C)C)([CH3:14])[CH3:13].[Li+].[CH2:20](Br)[CH:21]=[CH2:22]>C1COCC1>[CH2:14]([C:8]1([CH2:22][CH:21]=[CH2:20])[C:7](=[O:10])[N:6]2[C:2]([CH3:11])([CH3:1])[O:3][CH2:4][C@H:5]2[CH2:9]1)[CH:12]=[CH2:13]

Participants

5

Reactant 3

HCID 7841Allyl bromide2×HCID 2724682Lithium diisopropylamide2×HCID 137469293H,5H-Pyrrolo[1,2-c]oxazol-5-one, tetrahydro-3,3-dimethyl-, (R)-

Product 1

HCID 118342901HCID 118342901, compoundYield 86%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (R)-3,3-dimethyltetrahydropyrrolo[1,2-c]oxazol-5(3H)-one (2.55 g, 16.43 mmol) in THF (54.8 ml) cooled to −78° C., was added lithium diisopropylamide (14.79 ml, 29.6 mmol) solution. The solution was stirred at this temperature for 1 h before adding allyl bromide (2.133 ml, 24.65 mmol). The reaction mixture was warmed to rt (1 h) then cooled to −78° C. prior addition of lithium diisopropylamide (14.79 ml, 29.6 mmol). The mixture was stirred at −78° C. for 1 h before adding allyl bromide (2.133 ml, 24.65 mmol). The mixture was slowly warm to rt and stirred overnight. The reaction was quenched with sat. NH4Cl and extracted with EtOAc. The combined extracts were washed with brine, dried and concentrated. The crude material was absorbed onto a plug of silica gel and purified by chromatography through a REDISEP™ pre-packed silica gel column (80 g), eluting with a gradient of 0% to 25% EtOAc in hexane, to provide (R)-6,6-diallyl-3,3-dimethyltetrahydropyrrolo[1,2-c]oxazol-5(3H)-one (3.31 g, 14.07 mmol, 86% yield) as light-yellow oil. 1H NMR (400 MHz, CDCl3) δ 5.66-5.90 (m, 2H), 5.06-5.19 (m, 4H), 4.01-4.11 (m, 2H), 3.29-3.38 (m, 1H), 2.32-2.48 (m, 2H), 2.20-2.29 (m, 1H), 2.12 (dd, J=8.97, 13.79 Hz, 1H), 1.86-1.98 (m, 1H), 1.73-1.84 (m, 1H), 1.65 (s, 3H), 1.46 (s, 3H).

Workup

  1. temperaturethen cooled to −78° C.
  2. stirringThe mixture was stirred at −78° C. for 1 h
  3. temperatureThe mixture was slowly warm to rt
  4. stirringstirred overnight
  5. customThe reaction was quenched with sat. NH4Cl
  6. extractionextracted with EtOAc
  7. washThe combined extracts were washed with brine
  8. customdried
  9. concentrationconcentrated
  10. customThe crude material was absorbed onto a plug of silica gel
  11. custompurified by chromatography through a REDISEP™ pre-packed silica gel column (80 g)
  12. washeluting with a gradient of 0% to 25% EtOAc in hexane

Sources & evidence

ORD record
ord-fd6aec71fd26451b8c5b5ddaaf5e9150
Source dataset
uspto-grants-2016_06
Patent number
US09365522B2

Reaction notes

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