Diisopropylamine → HCID 13868632, compound

HRID 2285363Notes

Reaction equation

HRID 2285363 reaction equation
[CH:1](NC(C)C)(C)[CH3:2].C([Li])CCC.[CH3:13][CH:14]1[CH2:18][CH2:17][O:16][C:15]1=[O:19].C(Br)=C>O1CCCC1>[CH3:13][C:14]1([CH:1]=[CH2:2])[CH2:18][CH2:17][O:16][C:15]1=[O:19]

Participants

6

Reactant 4

HCID 7912DiisopropylamineHCID 11641BromoetheneHCID 98323alpha-MethylbutyrolactoneHCID 178418339Butyllithium

Product 1

HCID 13868632HCID 13868632, compoundYield 48%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

A cooled (−78° C.) solution of N,N-diisopropylamine (4.7 mL, 33.815 mmol, dried over calcium hydride) in anhydrous tetrahydrofuran (20 mL) was treated with a solution of n-butyllithium in hexanes (12.7 mL, 31.702 mmol, 2.5 M). After stirring at −78° C. for 25 minutes, the mixture was treated with 3-methyl-dihydro-furan-2-one (2 mL, 21.135 mmol). After stirring at 0° C. for 1 h, the reaction was subsequently treated with a solution of di-μ-bromobis(tri-tert-butylphosphino)dipalladium(I) (164.2 mg, 0.211 mmol) in anhydrous tetrahydrofuran (5 mL) and a solution of vinyl bromide in tetrahydrofuran (31.7 mL, 81.702 mmol, 1 M). The reaction was slowly warmed to room temperature. After stirring for 16 h, the reaction was quenched with hydrochloric acid (2 M) and water. The aqueous layer was extracted with diethyl ether (2×). The organics were combined, dried over anhydrous sodium sulfate, filtered and the volatiles were removed in vacuo. The residue was purified by silica gel chromatography using a 100 g Isolute cartridge eluted with a continuous gradient of iso-hexanes/diethyl ether 1:0 to 3:2 to afford the title compound (1.272 g, 48%) as an orange oil. 1H NMR (300 MHz, CDCl3) δ 1.38 (s, 3H), 2.11-2.22 (m, 1H), 2.31-2.41 (m, 1H), 4.20-4.36 (m, 2H), 5.16-5.26 (m, 2H), 5.84-5.96 (m, 1H).

Workup

  1. stirringAfter stirring at 0° C. for 1 h
  2. temperatureThe reaction was slowly warmed to room temperature
  3. stirringAfter stirring for 16 h
  4. customthe reaction was quenched with hydrochloric acid (2 M) and water
  5. extractionThe aqueous layer was extracted with diethyl ether (2×)
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. customthe volatiles were removed in vacuo
  9. customThe residue was purified by silica gel chromatography
  10. washeluted with a continuous gradient of iso-hexanes/diethyl ether 1:0 to 3:2

Sources & evidence

ORD record
ord-7ef5cfbd6fe94f53ba9d4619046884ef
Source dataset
uspto-grants-2015_09
Patent number
US09145441B2

Reaction notes

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