Diethyl Ether → HCID 10063225, compound

HRID 2050943Notes

Reaction equation

HRID 2050943 reaction equation
C(O[C:4]1[CH2:5][C@@H:6]([CH2:11][C@H:12]2[N:16]([CH2:17][C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C:15](=[O:24])[CH2:14][CH2:13]2)[CH2:7][C:8](=[O:10])[CH:9]=1)C.[CH3:25]COCC.C[Li]>O1CCCC1>[CH3:25][C:4]1[CH2:5][C@H:6]([CH2:11][C@H:12]2[N:16]([CH2:17][C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C:15](=[O:24])[CH2:14][CH2:13]2)[CH2:7][C:8](=[O:10])[CH:9]=1

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 10245891HCID 10245891, compoundHCID 178418348HCID 178418348, compound

Product 1

HCID 10063225HCID 10063225, compoundYield 52%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of (5S,1R)-5-[(3-ethoxy-5-oxo-3-cyclohexen-1-yl)methyl]-1-(phenylmethyl)-2-pyrrolidinone (3.94 g, 12.0 mmol) in 150 ml of 1:1 tetrahydrofuran:ether was added a solution of methyllithium (41 mL, 1.4M in ether, 57.4 mmol) at -78° C. over 10 min. The mixture was stirred for 30 min at -78° C. and quenched by the addition of 50 mL of 50% aqueous acetic acid. The mixture was allowed to warm to room temperature and was extracted with methylene chloride. The combined extracts were washed with saturated sodium bicarbonate, dried over Na2SO4 and concentrated on a rotary evaporator to give 4.05 g of a crude oil. Chromatography of the crude product on silica gel (100 g) eluting with 1% methanol in ethyl acetate afforded 1.85 g (52% yield) of (5S,1R)-5-[(3-methyl-5-oxo-3-cyclohexen- 1-yl)methyl]-1-(phenylmethyl)-2-pyrrolidinone as an oil. A sample was evaporatively distilled at 200°-210° C./0.05 torr for analysis. 1H NMR (CDCl3) δ 1.94 (s, 3 H, CH3), 1.35-2.55 (m, 11 H, CH2 and CH), 3.45 (m, 1 H, NCH), 3.95 and 4.98 (AB,Jgem =15 Hz, 2 H, CH2Ph), 3.87 (s, 1 H, vinyl H), 7.50 (m, 5 H, phenyl). MS (EI) m/e 297 (M+). [α]25D =+59.86°(c 0.2155 in methanol). CD (ethanol) 326 ([ϑ]=-1425, max), 283 ([ϑ]=-42, min), 238 ([ϑ]=+13,620, infl), 218 ([ϑ]=+50,100, max), 212 nm ([ϑ]=+39,820°, min). Anal. Calcd for C19H23NO2 : C, 76.74; H, 7.80; N, 4.71. Found: C, 74.55; H, 7.53, N, 7.41.

Workup

  1. customquenched by the addition of 50 mL of 50% aqueous acetic acid
  2. temperatureto warm to room temperature
  3. extractionwas extracted with methylene chloride
  4. washThe combined extracts were washed with saturated sodium bicarbonate
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated on a rotary evaporator
  7. customto give 4.05 g of a crude oil
  8. washChromatography of the crude product on silica gel (100 g) eluting with 1% methanol in ethyl acetate

Sources & evidence

ORD record
ord-bf6fd57cc08d4e0690e9b6bdd15a517b
Source dataset
uspto-grants-1991_05
Patent number
US05015653

Reaction notes

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