Triacetoxyperiodinane → 1-Oxo-1-[5-(2-pyridyl)oxazol-2-yl]-7-(3-chlorophenyl)heptane

HRID 1645329Notes

Reaction equation

HRID 1645329 reaction equation
[O:1]=[C:2]([C:16]1[O:17][C:18]([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][N:22]=2)=[CH:19][N:20]=1)[CH2:3][CH2:4][CH2:5][CH2:6][C:7]#[C:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([Cl:15])[CH:10]=1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C1COCC1.[Ni]>[O:1]=[C:2]([C:16]1[O:17][C:18]([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][N:22]=2)=[CH:19][N:20]=1)[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([Cl:15])[CH:10]=1

Participants

5

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 16737627Oxo-1-[5-(2-pyridyl)oxazol-2-yl]-7-(3-chlorophenyl)hept-6-yne

Product 1

HCID 167364471-Oxo-1-[5-(2-pyridyl)oxazol-2-yl]-7-(3-chlorophenyl)heptaneYield 67%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
25 °C

Procedure

A solution of the oxo-1-[5-(2-pyridyl)oxazol-2-yl]-7-(3-chlorophenyl)hept-6-yne (4hh, 15 mg, 0.041 mmol) in anhydrous THF (1 mL) was treated with a catalytic amount of Raney nickel (washed before use with THF). The reaction mixture was purged with H2 and stirred at 25° C. overnight. The suspension was filtered through Celite and concentrated. The crude product was dissolved in anhydrous CH2Cl2 (2 mL) and treated with Dess-Martin reagent (29 mg, 0.068 mmol). After stirring for 3 h at 25° C., the reaction mixture was quenched with saturated aqueous Na2CO3 and saturated aqueous Na2S2O3. After stirring for 15 min, the mixture was extracted with CH2Cl2. The organic layer was dried over Na2SO4, filtered and concentrated. PTLC (SiO2, 40% EtOAc-hexanes) afforded the title compound (5hh, 10 mg, 0.027 mmol, 67%) as a white solid: mp 91-92° C.; 1H NMR (CDCl3, 600 MHz) 8.68-8.66 (m, 1H), 7.89-7.86 (m, 2H), 7.82 (td, 1H, J=7.8, 1.4 Hz), 7.34-7.31 (m, 1H), 7.21-7.14 (m, 3H), 7.04 (d, 1H, J=7.5 Hz), 3.11 (t, 2H, J=7.4 Hz), 2.59 (t, 2H, J=7.4 Hz), 1.81-1.76 (m, 2H), 1.65-1.60 (m, 2H), 1.46-1.36 (m, 4H); 13C NMR (CDCl3, 125 MHz) 188.4, 157.3, 153.2, 150.1, 146.3, 144.7, 137.1, 133.9, 129.5, 128.5, 126.8, 126.6, 124.1, 120.4, 39.0, 35.5, 31.0, 28.9, 28.8, 23.8; IR (film) νmax 2930, 2856, 1698, 1601, 1575, 1505, 1470, 1426, 1385, 1285, 1081, 1035, 990, 962, 935, 783, 741, 696 cm−1; ESI-TOF m/z 369.1363 (C21H21ClN2O2+H+ requires 369.1364).

Workup

  1. customThe reaction mixture was purged with H2
  2. filtrationThe suspension was filtered through Celite
  3. concentrationconcentrated
  4. dissolutionThe crude product was dissolved in anhydrous CH2Cl2 (2 mL)
  5. stirringAfter stirring for 3 h at 25° C.
  6. customthe reaction mixture was quenched with saturated aqueous Na2CO3 and saturated aqueous Na2S2O3
  7. stirringAfter stirring for 15 min
  8. extractionthe mixture was extracted with CH2Cl2
  9. dry with materialThe organic layer was dried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-0ada439a10624018b0a0dcd65f29667a
Source dataset
uspto-grants-2012_02
Patent number
US08124778B2

Reaction notes

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