Water → HCID 86724639, compound

HRID 707725Notes

Reaction equation

HRID 707725 reaction equation
[CH3:1][C@H:2]([C:18]([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)=C)[C@H:3]([NH:11][C:12](=[O:17])[C:13]([F:16])([F:15])[F:14])[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5].C[N+]1([O-])CC[O:30]CC1.O>C1COCC1.CCOC(C)=O.O=[Os](=O)(=O)=O>[CH3:1][C@@H:2]([C:18](=[O:30])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C@H:3]([NH:11][C:12](=[O:17])[C:13]([F:16])([F:15])[F:14])[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5]

Participants

7

Reactant 3

HCID 962WaterHCID 82029Methyl morpholine oxideHCID 53355013HCID 53355013, compound

Product 1

HCID 86724639HCID 86724639, compound

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To olefin 16 (903.4 mg, 2.53 mmol) in THF (25 mL) under N2 was added NMO (60% wt solution in H2O, 0.90 mL, 5.06 mmol) and OsO4 (4% wt solution in H2O, 1.50 mL, 0.25 mmol). The solution was stirred at ambient temperature for 16 h, and NaIO4 (2.16 g, 10.12 mmol) was then added, followed by H2O (2.7 mL). Stirring was continued for 4 h, and the reaction mixture was then diluted with EtOAc (200 mL) and washed with 10% Na2S2O3 (4×50 mL). The combined washings were extracted with EtOAc (50 mL). The organic solutions were combined and washed with 5 M NaCl (20 mL) and dried, and the solvent was evaporated. The residue was separated by chromatography (silica gel, 30 g; 9:1 hexane-EtOAc) and led to 0.632 g (70%) of 18 as a colorless solid: mp 127-128° C.; Rf0.19 (95:5 hexane-EtOAc); [α]23D−39.0 (c 1.05, CH3OH); 1H NMR δ 7.92 (2H, dd, J=7.5 and 1.3 Hz), 7.60 (1H, tt, J=7.5 and 1.3 Hz), 7.49 (2H, t, J=7.6 Hz), 7.03 (1H, br d, J=6.7 Hz), 4.72 (1H, dd, J=7.4 and 4.8 Hz), 4.13 (1H, m), 1.49 (9H, s), 1.36 (3H, d, J=7.2 Hz); 13C NMR δ 200.0, 168.3, 156.9 (q), 135.5, 133.6, 128.8, 128.4, 83.8, 55.0, 42.9, 27.8, 14.2; MS APCI+ m/z 360.1417 [M+H]+ (calcd for C17H21F3NO4, 360.1423); anal. C, 56.39%, H, 5.60%, N, 3.96%, calcd for C17H20F3NO4, C, 56.82%, H, 5.61%, N, 3.90%.

Workup

  1. stirringStirring
  2. waitwas continued for 4 h
  3. washwashed with 10% Na2S2O3 (4×50 mL)
  4. extractionThe combined washings were extracted with EtOAc (50 mL)
  5. washwashed with 5 M NaCl (20 mL)
  6. customdried
  7. customthe solvent was evaporated
  8. customThe residue was separated by chromatography (silica gel, 30 g; 9:1 hexane-EtOAc)

Sources & evidence

ORD record
ord-7ac06c5e627b4a8787a92638621e02bc
Source dataset
uspto-grants-2015_11
Patent number
US09175041B2

Reaction notes

Loading…