Sodium Thiosulfate → N-(4-(((tert-butyldiphenylsilyl)oxy)methyl)-2-iodo-5-(methylsulfonyl)phenyl)methanesulfonamide

HRID 1468908Notes

Reaction equation

HRID 1468908 reaction equation
[Si:1]([O:18][CH2:19][C:20]1[C:25](SC)=[CH:24][C:23]([NH:28][S:29]([CH3:32])(=[O:31])=[O:30])=[C:22]([I:33])[CH:21]=1)([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH:34]1C=C(Cl)C=C(C(OO)=O)C=1.C([O-])(O)=O.[Na+].[O-][S:51]([O-:54])(=S)=[O:52].[Na+].[Na+]>C(Cl)Cl>[Si:1]([O:18][CH2:19][C:20]1[C:25]([S:51]([CH3:34])(=[O:54])=[O:52])=[CH:24][C:23]([NH:28][S:29]([CH3:32])(=[O:31])=[O:30])=[C:22]([I:33])[CH:21]=1)([C:14]([CH3:17])([CH3:15])[CH3:16])([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

6

Reactant 4

HCID 24477Sodium ThiosulfateHCID 70297m-Chloroperbenzoic acidHCID 516892Sodium BicarbonateHCID 89814652N-(4-(((tert-butyldiphenylsilyl)oxy)methyl)-2-iodo-5-(methylthio)phenyl)methanesulfonamide

Product 1

HCID 89814617N-(4-(((tert-butyldiphenylsilyl)oxy)methyl)-2-iodo-5-(methylsulfonyl)phenyl)methanesulfonamideYield 80%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A suspension of crude N-(4-(((tert-butyldiphenylsilyl)oxy)methyl)-2-iodo-5-(methylthio)phenyl)methanesulfonamide and mCPBA (8.9 g, 51.6 mmol) in CH2Cl2 (100 mL) was stirred for 2 h at rt. Sat. aq. NaHCO3 (50 mL) and Na2S2O3 (50 mL) were added and the layers separated. The aqueous layer was extracted with CH2Cl2 (2×100 mL). The combined organic layers were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography over silica gel eluting with EtOAc/hexanes (3/7) to provide N-(4-(((tert-butyldiphenylsilyl)oxy)methyl)-2-iodo-5-(methylsulfonyl)phenyl)methanesulfonamide (8.8 g, 80% yield for two steps). For N-(4-(((tert-butyldiphenylsilyl)oxy)methyl)-2-iodo-5-(methylthio)phenyl)methanesulfonamide: LC-MS m/z 612 [M+H]+. For N-(4-(((tert-butyldiphenylsilyl)oxy)methyl)-2-iodo-5-(methylsulfonyl)phenyl)methanesulfonamide: LC-MS m/z 644 [M+H]+. 1H NMR (400 MHz, CDCl3): δ 8.25 (s, 1H), 8.08 (s, 1H), 7.67-7.65 (m, 4H), 7.46-7.37 (m, 6H), 6.77 (s, 1H), 5.05 (s, 2H), 3.11 (s, 3H), 2.83 (s, 3H), 1.12 (s, 9H).

Workup

  1. customthe layers separated
  2. extractionThe aqueous layer was extracted with CH2Cl2 (2×100 mL)
  3. dry with materialThe combined organic layers were dried over anhydrous Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by flash chromatography over silica gel eluting with EtOAc/hexanes (3/7)

Sources & evidence

ORD record
ord-00cd62292a894e689109c8a42b5a8885
Source dataset
uspto-grants-2015_04
Patent number
US09006244B2

Reaction notes

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