Iodide Ion → (2-{3-Benzyloxy-4-[1,1,4-trioxo-5-(2-trimethylsilanylethyl)-1,2,5-thiadiazolidin-2-yl]-phenyl}-ethyl)-carbamic Acid Tert-butyl Ester

HRID 660520Notes

Reaction equation

HRID 660520 reaction equation
[C:1]([O:5][C:6](=[O:11])[NH:7][CH2:8][CH2:9]I)([CH3:4])([CH3:3])[CH3:2].[I-].[CH2:13]([O:20][C:21]1[CH:26]=[C:25](I)[CH:24]=[CH:23][C:22]=1[N:28]1[S:32](=[O:34])(=[O:33])[N:31]([CH2:35][CH2:36][Si:37]([CH3:40])([CH3:39])[CH3:38])[C:30](=[O:41])[CH2:29]1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>CN(C=O)C.CCOC(C)=O.[Zn]>[C:1]([O:5][C:6](=[O:11])[NH:7][CH2:8][CH2:9][C:25]1[CH:24]=[CH:23][C:22]([N:28]2[CH2:29][C:30](=[O:41])[N:31]([CH2:35][CH2:36][Si:37]([CH3:40])([CH3:39])[CH3:38])[S:32]2(=[O:34])=[O:33])=[C:21]([O:20][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH:26]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

7

Reactant 3

HCID 30165Iodide IonHCID 641024tert-butyl N-(2-iodoethyl)carbamateHCID 667569375-(2-Benzyloxy-4-iodophenyl)-1,1-dioxo-2-(2-trimethylsilanylethyl)-1,2,5-thiadiazolidin-3-one

Product 1

HCID 68842331(2-{3-Benzyloxy-4-[1,1,4-trioxo-5-(2-trimethylsilanylethyl)-1,2,5-thiadiazolidin-2-yl]-phenyl}-ethyl)-carbamic Acid Tert-butyl Ester

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Zinc dust (3 g, 46 mmol) is placed in a flask and heated under vacuum to remove traces of water. DMF (25 mL) is then added under nitrogen atmosphere. Dibromoethane (cat. 0.25 mL) is added and the mixture heated until effervescence occurs. The reaction is allowed to cool to RT over 30 min and chlorotrimethylsilane (cat 0.3 mL) is added, followed after 30 min with (2-iodoethyl)-carbamic acid tert-butyl ester (4.5 g, 16.5 mmol) dissolved in 10 mL of DMF. After 30 min, TLC indicates the iodide has been consumed and Pd2(dba)3 (0.20 g) and tri-o-tolylphosphine (0.30 g) are added, followed by the dropwise addition of 5-(2-benzyloxy-4-iodophenyl)-1,1-dioxo-2-(2-trimethylsilanylethyl)-1,2,5-thiadiazolidin-3-one (5 g, 9.2 mmol) dissolved in 25 mL of DMF. The reaction mixture is stirred for 14 h and then diluted with EtOAc and filtered through Celite. The filtrate is washed with 1M HCl, brine and water, dried over MgSO4, filtered through a short plug of silica and concentrated to afford the title compound as a light yellow oil.

Workup

  1. temperatureheated under vacuum
  2. customto remove traces of water
  3. additionDMF (25 mL) is then added under nitrogen atmosphere
  4. additionDibromoethane (cat. 0.25 mL) is added
  5. temperaturethe mixture heated until effervescence
  6. additionchlorotrimethylsilane (cat 0.3 mL) is added
  7. customhas been consumed
  8. additionPd2(dba)3 (0.20 g) and tri-o-tolylphosphine (0.30 g) are added
  9. filtrationfiltered through Celite
  10. washThe filtrate is washed with 1M HCl, brine and water
  11. dry with materialdried over MgSO4
  12. filtrationfiltered through a short plug of silica
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-b4ff4d06c34440f182cf7dc28b42a4c8
Source dataset
uspto-grants-2011_12
Patent number
US08084448B2

Reaction notes

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