Cesium carbonate → Benzyl 17-methyl-2,5,8,11-tetraoxa-14-thiaoctadecan-17-ylcarbamate

HRID 1770723Notes

Reaction equation

HRID 1770723 reaction equation
[SH:1][CH2:2][CH2:3][C:4]([NH:7][C:8](=[O:17])[O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)([CH3:6])[CH3:5].C(=O)([O-])[O-].[Cs+].[Cs+].Br[CH2:25][CH2:26][O:27][CH2:28][CH2:29][O:30][CH2:31][CH2:32][O:33][CH2:34][CH2:35][O:36][CH3:37]>CN(C)C=O>[CH3:5][C:4]([NH:7][C:8](=[O:17])[O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)([CH3:6])[CH2:3][CH2:2][S:1][CH2:25][CH2:26][O:27][CH2:28][CH2:29][O:30][CH2:31][CH2:32][O:33][CH2:34][CH2:35][O:36][CH3:37]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 1938913213-Bromo-2,5,8,11-tetraoxatridecaneHCID 86665509Benzyl 4-mercapto-2-methylbutan-2-ylcarbamate

Product 1

HCID 67509261Benzyl 17-methyl-2,5,8,11-tetraoxa-14-thiaoctadecan-17-ylcarbamateYield 98.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of benzyl 4-mercapto-2-methylbutan-2-ylcarbamate (20 mmol) in N,N-dimethylformamide (20 ml) was added cesium carbonate (6.49 g, 19.9 mmol) and 13-bromo-2,5,8,11-tetraoxatridecane (5.00 g, 18.4 mmol). The solution was stirred for 16 hours, concentrated in vacuo, and the residue dissolved in 500 ml ethylacetate, washed with 3 times with 100 ml 5% NaHSO4, 1×200 ml sat. NaCl, dried on MgSO4, and concentrated in vacuo. The residue was purified by flash chromatography (10% to 60% ethylacetate in hexanes) to give the titled compound as a clear oil (7.47 g, 18.1 mmol, 98%). 1H NMR (400 MHz, CDCl3) δ 1.31 (s, 6H), 1.95-1.99 (m, 2H), 2.51-2.55 (m, 2H), 2.69-2.73 (m, 2H), 3.38 (s, 3H), 3.54-3.58 (m, 2H, 3.6-3.7 (m, 14H), 4.77 (br s, 1H), 5.06 (s, 2H), 7.3-7.4 (m, 5H). LRMS (ESI/APCI): 466 [M+Na]+.

Workup

  1. concentrationconcentrated in vacuo
  2. dissolutionthe residue dissolved in 500 ml ethylacetate
  3. washwashed with 3 times with 100 ml 5% NaHSO4, 1×200 ml sat. NaCl
  4. customdried on MgSO4
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by flash chromatography (10% to 60% ethylacetate in hexanes)

Sources & evidence

ORD record
ord-5ae3745b241e49989032acbc6edbd7df
Source dataset
uspto-grants-2016_02
Patent number
US09248117B2

Reaction notes

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