Triacetoxyperiodinane → 1-(6-(1-methyl-1H-pyrazol-4-yl)benzo[d]thiazol-2-yl)azetidin-3-one

HRID 2040951Notes

Reaction equation

HRID 2040951 reaction equation
[CH3:1][N:2]1[CH:6]=[C:5]([C:7]2[CH:20]=[CH:19][C:10]3[N:11]=[C:12]([N:14]4[CH2:17][CH:16]([OH:18])[CH2:15]4)[S:13][C:9]=3[CH:8]=2)[CH:4]=[N:3]1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.CC(C)=O.CS(C)=O>C(OCC)C>[CH3:1][N:2]1[CH:6]=[C:5]([C:7]2[CH:20]=[CH:19][C:10]3[N:11]=[C:12]([N:14]4[CH2:15][C:16](=[O:18])[CH2:17]4)[S:13][C:9]=3[CH:8]=2)[CH:4]=[N:3]1

Participants

5

Reactant 3

HCID 159087Triacetoxyperiodinane2×HCID 21922538Acetone dimethyl sulfoxideHCID 669055801-(6-(1-methyl-1H-pyrazol-4-yl)benzo[d]thiazol-2-yl)azetidin-3-ol

Product 1

HCID 669058091-(6-(1-methyl-1H-pyrazol-4-yl)benzo[d]thiazol-2-yl)azetidin-3-one

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A suspension of 1-(6-(1-methyl-1H-pyrazol-4-yl)benzo[d]thiazol-2-yl)azetidin-3-ol (Reference Example 2, 0.143 g, 0.50 mmol) and Dess-Martin periodinane (1,1,1-tris(acetyloxy)-1,1-dihydro-1,2-benziodoxol-3-(1H)-one, CAS #87413-09-0, 0.636 g, 1.50 mmol) was stirred in 15:1 acetone/dimethyl sulfoxide (15 mL/1 mL). The reaction mixture was heated to near reflux for 4 hours, then additional Dess-Martin periodinane (0.212 g, 0.50 mmol) was added. The reaction was cooled to room temperature after an additional 3 hours of heating at near reflux. The reaction mixture was diluted with diethyl ether (15 mL) and insoluble material was removed by filtration. The filtrate was concentrated under reduced pressure to remove all but the dimethyl sulfoxide. This residue was partitioned between 9:1 CH2Cl2/hexane (20 mL) and water (10 mL). The organic layer was dried (Na2SO4) and filtered. The filtrate was concentrated under reduced pressure and the residue was purified by silica gel chromatography (90:10 to 40:60 CH2Cl2/ethyl acetate). Fractions containing product were combined and concentrated under reduced pressure to give a gummy solid, which after trituration with diethyl ether, provided 1-(6-(1-methyl-1H-pyrazol-4-yl)benzo[d]thiazol-2-yl)azetidin-3-one as a solid. 1H NMR (300 MHz, CDCl3) δ ppm 3.95 (s, 3H), 5.00 (s, 4H), 7.46 (dd, J=2, 8 Hz, 1H), 7.59 (s, 1H), 7.64 (d, J=8 Hz, 1H), 7.74 (d, J=2 Hz, 1H), 7.75 (s, 1H); MS (DCI/NH3) m/z 285 (M+H)+.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto near reflux for 4 hours
  3. temperatureof heating at near reflux
  4. customwas removed by filtration
  5. concentrationThe filtrate was concentrated under reduced pressure
  6. customto remove all but the dimethyl sulfoxide
  7. customThis residue was partitioned between 9:1 CH2Cl2/hexane (20 mL) and water (10 mL)
  8. dry with materialThe organic layer was dried (Na2SO4)
  9. filtrationfiltered
  10. concentrationThe filtrate was concentrated under reduced pressure
  11. customthe residue was purified by silica gel chromatography (90:10 to 40:60 CH2Cl2/ethyl acetate)
  12. additionFractions containing product
  13. concentrationconcentrated under reduced pressure
  14. customto give a gummy solid, which after trituration with diethyl ether

Sources & evidence

ORD record
ord-607f4ef64d5f420c93943c9e255df063
Source dataset
uspto-grants-2013_11
Patent number
US08580968B2

Reaction notes

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