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

HRID 1482964Notes

Reaction equation

HRID 1482964 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, 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). 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 materialCombined 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-98fb07ffba1442d19a1a9a9f8bb62cc0
Source dataset
uspto-grants-2016_08
Patent number
US09416135B2

Reaction notes

Loading…