HCID 90408321, compound → HCID 90409183, compound

HRID 1855086Notes

Reaction equation

HRID 1855086 reaction equation
[Li][CH2:2]CCC.[O:6]([C:13]1[CH:14]=[C:15]([C:19]23[CH2:26][CH2:25][C:22]([CH2:27][CH2:28][CH2:29][CH:30]=O)([CH2:23][CH2:24]2)[CH2:21][O: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.CCCCCC>[CH2:27]([C:22]12[CH2:25][CH2:26][C:19]([C:15]3[CH:16]=[CH:17][CH:18]=[C:13]([O:6][C:7]4[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=4)[CH:14]=3)([CH2:24][CH2:23]1)[O:20][CH2:21]2)[CH2:28][CH2:29][CH:30]=[CH2:2]

Participants

6

Reactant 2

HCID 90408321HCID 90408321, compoundHCID 178418339Butyllithium

Product 1

HCID 90409183HCID 90409183, compoundYield 81%

Reagents, catalysts & solvents 3

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

To a 0° C. mixture of methyl triphenylphosphonium bromide (236 mg, 0.66 mmol) in THF (8 mL) was added dropwise n-BuLi (0.27 mL of a 2.5 M solution in hexane, 0.66 mmol). The reaction mixture was stirred at 0° C. for 30 min, and a solution of 4-(1-(3-phenoxyphenyl)-2-oxabicyclo[2.2.2]octan-4-yl)butanal (116 mg, 0.33 mmol) in THF (2 mL) was added at 0° C. The reaction mixture was warmed to rt and stirred for 2 h, then was quenched with sat′d aq. NH4Cl, and extracted with EtOAc. The organic layer was washed with brine, dried (MgSO4), and concentrated in vacuo. The crude material was purified by flash chromatography (SiO2; gradient from 0 to 30% EtOAc:hexanes) to afford the title compound as a colorless oil (94 mg; 81% yield). 1H NMR (400 MHz, CDCl3) δ 7.34-7.23 (m, 4H), 7.16-7.05 (m, 2H), 6.98 (dd, J=8.7, 1.0 Hz, 2H), 6.83 (ddd, J=8.0, 2.4, 1.0 Hz, 1H), 5.79 (ddt, J=17.0, 10.3, 6.6 Hz, 1H), 5.03-4.93 (m, 1H), 3.79 (s, 2H), 2.06-1.93 (m, 5H), 1.70-1.52 (m, 6H), 1.48-1.22 (m, 3H), 1.21-1.03 (m, 2H).

Workup

  1. temperatureThe reaction mixture was warmed to rt
  2. stirringstirred for 2 h
  3. customwas quenched with sat′d aq. NH4Cl
  4. extractionextracted with EtOAc
  5. washThe organic layer was washed with brine
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated in vacuo
  8. customThe crude material was purified by flash chromatography (SiO2; gradient from 0 to 30% EtOAc:hexanes)

Sources & evidence

ORD record
ord-48bf14513def4f949a472fb13160f9b9
Source dataset
uspto-grants-2015_02
Patent number
US08962660B2

Reaction notes

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