HCID 90409093, compound → HCID 90408476, compound

HRID 1855065Notes

Reaction equation

HRID 1855065 reaction equation
[CH2:1]([Li])CCC.[O:6]([C:13]1[CH:14]=[C:15]([C:19]23[CH2:26][CH2:25][C:22]([CH:27]=O)([CH2:23][CH2:24]2)[O:21][CH2:20]3)[CH:16]=[CH:17][CH:18]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[O:6]([C:13]1[CH:14]=[C:15]([C:19]23[CH2:26][CH2:25][C:22]([CH:27]=[CH2:1])([CH2:23][CH2:24]2)[O:21][CH2:20]3)[CH:16]=[CH:17][CH:18]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

5

Reactant 2

HCID 90409093HCID 90409093, compoundHCID 178418339Butyllithium

Product 1

HCID 90408476HCID 90408476, compoundYield 61%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of (methyl)triphenylphosphonium bromide (80 mg, 0.224 mmol) in THF (1 mL) at 0° C. was added n-butyllithium (0.140 ml, 0.224 mmol). The reaction mixture was stirred at 0° C. for 30 min. A solution of 4-(3-Phenoxyphenyl)-2-oxabicyclo[2.2.2]octane-1-carbaldehyde (23 mg, 0.075 mmol) in THF (0.5 mL) was then added at 0° C. The reaction was warmed to rt and stirred for 4 h. The reaction was then quenched with saturated aq. NH4Cl, diluted with EtOAc, washed with water and brine, dried (MgSO4), filtered, and concentrated in vacuo. The residue was purified by flash chromatography on SiO2 (0 to 50% EtOAc:hexanes) to afford the title compound (14 mg, 61% yield) as a colorless oil. 1H NMR (500 MHz, CDCl3) δ 7.37-7.29 (m, 3H), 7.14-7.10 (m, 1H), 7.01 (d, J=7.7 Hz, 4H), 6.84 (ddd, J=8.0, 2.4, 0.8 Hz, 1H), 5.89 (dd, J=17.5, 10.9 Hz, 1H), 5.20 (d, J=17.3 Hz, 1H), 5.07 (d, J=10.7 Hz, 1H), 4.08-4.03 (m, 2H), 2.13-1.91 (m, 6H), 1.87-1.80 (m, 2H).

Workup

  1. temperatureThe reaction was warmed to rt
  2. stirringstirred for 4 h
  3. customThe reaction was then quenched with saturated aq. NH4Cl
  4. additiondiluted with EtOAc
  5. washwashed with water and brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by flash chromatography on SiO2 (0 to 50% EtOAc:hexanes)

Sources & evidence

ORD record
ord-093a5d10ec4b41e986cfa721e676239b
Source dataset
uspto-grants-2015_02
Patent number
US08962660B2

Reaction notes

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