Phthalimide → HCID 9926035, compound

HRID 1060708Notes

Reaction equation

HRID 1060708 reaction equation
[C:1]1(=[O:11])[NH:5][C:4](=[O:6])[C:3]2=[CH:7][CH:8]=[CH:9][CH:10]=[C:2]12.[CH2:12]1[CH2:16][O:15][CH2:14][CH2:13]1>C[C@@H](N(C)C)[C]1[C](P(C2C=CC=CC=2)C2C=CC=CC=2)[CH][CH][CH]1.C1C=CC(P([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.[Fe].O>[OH:15][C@@H:16]1[C:12]2[C:2](=[CH:10][CH:9]=[CH:14][CH:13]=2)[CH:3]=[CH:7][C@H:8]1[N:5]1[C:1](=[O:11])[C:2]2[C:3](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:4]1=[O:6]

Participants

5

Reactant 2

HCID 6809PhthalimideHCID 8028Tetrahydrofuran

Product 1

HCID 9926035HCID 9926035, compoundYield 52%

Reagents, catalysts & solvents 2

HCID 178461695HCID 178461695, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

To a flame dried round bottom flask, [Rh(COD)Cl]2 (5.4 mg, 0.011 mmol), (R)-(S)-BPPFA (12.2 mg, 0.022 mmol), phthalimide (510 mg, 3.47 mmol) and 1 (100 mg, 0.69 mmol) were added. THF (4 mL) was then added, followed by heating to 80° C. for 3 days. The reaction mixture was then poured in to water and extracted three times with ethyl acetate. The organic layers were combined, washed with brine dried over Na2SO4, and concentrated in vacuo. The resulting solid was purified by flash chromatography (30% ethyl acetate in hexanes) to give 2 as a white crystalline solid (103.5 mg, 52%). The ee was determined to be 74% using, HPLC analysis on a CHIRALCEL OD column, λ=486 nm. Retention times in 10% isopropanol in hexanes were 21.1 min (major)and 29.1 min. Rf=0.36 on silica gel (30% ethyl acetate:hexanes); mp 175-176° (dec); [α]25D=−6.1° (c=12.9, CHCl3); IR (KBr, cm−1) 3536 (br), 3067 (w), 2921 (w), 1772 (m), 1693 (s), 1388 (s), 1084 (m), 955 (m), 719 (s); 1H NMR (400 MHz, CDCl3) δ7.78-7.75 (2H, m), 7.68-7.64 (2H, m), 7.57-7.55 (1H, m), 7.26-7.22 (2H, m), 7.09-7.07 (1H, m), 6.51 (1H, dd, J=9.7, 2.7 Hz), 5.84 (1H, ddd, J=9.7. 2.7, 2.2 Hz), 5.48 (1H, d, J=12.8 Hz), 5.12 (1H, ddd, J=12.8, 2.5, 2.4 Hz), 2.82 (1H, s); 13C NMR (400 MHz, CDCl3) δ168.6, 137.3, 134.2, 132.6, 132.1, 128.7, 128.2, 128.1, 126.9, 126.5. 124.4, 123.5, 70.9, 55.3. HRMS calcd for C18H11NO2 (M+-H2O): 273.2939. Found: 273.0793.

Workup

  1. customTo a flame dried round bottom flask
  2. extractionextracted three times with ethyl acetate
  3. washwashed with brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated in vacuo
  6. customThe resulting solid was purified by flash chromatography (30% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-444940a430fb4bc88dd4b0ce95083c12
Source dataset
uspto-grants-2003_02
Patent number
US06525068B1

Reaction notes

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