Acetic Acid → HCID 118676928, compound

HRID 630545Notes

Reaction equation

HRID 630545 reaction equation
C([C@@H]1C[O:7]C(C2C=CC=CC=2NC2C(NC3C=CC=CC=3C3OC[C@@H](C(C)C)N=3)=CC=CC=2)=N1)(C)C.[CH:37]1([C:40]2[CH:45]=[CH:44][N:43]=[C:42]([C:46]3[CH:47]=[N:48][C:49]([N:52]4[C:60]5[C:55](=[CH:56][CH:57]=[C:58]([C:61]([O:63][CH3:64])=[O:62])[CH:59]=5)[C:54]([S:65][CH3:66])=[CH:53]4)=[N:50][CH:51]=3)[CH:41]=2)[CH2:39][CH2:38]1.C(O)(=O)C.OO>ClCCl>[CH:37]1([C:40]2[CH:45]=[CH:44][N:43]=[C:42]([C:46]3[CH:51]=[N:50][C:49]([N:52]4[C:60]5[C:55](=[CH:56][CH:57]=[C:58]([C:61]([O:63][CH3:64])=[O:62])[CH:59]=5)[C:54]([S:65]([CH3:66])=[O:7])=[CH:53]4)=[N:48][CH:47]=3)[CH:41]=2)[CH2:38][CH2:39]1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 784Hydrogen PeroxideHCID 118662817HCID 118662817, compoundHCID 118676831HCID 118676831, compound

Product 1

HCID 118676928HCID 118676928, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
6.5 °C

Procedure

N1,N2-bis(2-((R)-4-isopropyl-4,5-dihydrooxazol-2-yl)phenyl)benzene-1,2-diamine (6.95 mg, 0.014 mmol) and Mn(OTf)2 (5.09 mg, 0.014 mmol; for synthesis and application of this ligand see: Dai. W. et al. Org. Lett. 2013, 15, 5658; Dai. W. et al. Org. Lett. 2013, 15, 4138) in dichloromethane (10 mL) were stirred at room temperature for 3 h. 333a) (0.3 g, 0.721 mmol), acetic acid (0.263 mL, 4.61 mmol) and 30% aqueous hydrogen peroxide solution (0.147 mL, 1.47 mmol) were added at room temperature and the resulting mixture was immediately cooled with an ice bath to 5-8° C. The reaction mixture was stirred at this temperature for 30 min, quenched with saturated sodium sulfite solution (10 mL) and further stirred for 15 min. The mixture was then diluted with dichloromethane (30 mL) and washed with brine (20 mL). The combined organic layers were dried over sodium sulfate and evaporated. The residue was purified by flash column chromatography [silica; dichloromethane with 1.5% methanol]. White solid. Yield: 0.14 g (45% of theory). Enantiomeric excess: >99% (chiral HPLC)

Workup

  1. customfor synthesis and application of this ligand
  2. customquenched with saturated sodium sulfite solution (10 mL)
  3. stirringfurther stirred for 15 min
  4. additionThe mixture was then diluted with dichloromethane (30 mL)
  5. washwashed with brine (20 mL)
  6. dry with materialThe combined organic layers were dried over sodium sulfate
  7. customevaporated
  8. customThe residue was purified by flash column chromatography [silica; dichloromethane with 1.5% methanol]

Sources & evidence

ORD record
ord-fc09e876610d4412af4fdd08e7d1b935
Source dataset
uspto-grants-2016_04
Patent number
US09315490B2

Reaction notes

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