Cesium carbonate → Benzyl 14-methyl-2,5,8-trioxa-11-thiapentadecan-14-ylcarbamate

HRID 1770678Notes

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+].CC1C=CC(S(O[CH2:35][CH2:36][O:37][CH2:38][CH2:39][O:40][CH2:41][CH2:42][O:43][CH3:44])(=O)=O)=CC=1>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][CH2:35][CH2:36][O:37][CH2:38][CH2:39][O:40][CH2:41][CH2:42][O:43][CH3:44]

Participants

Conditions

Temperature: 60 °C

Procedure

To a solution of benzyl 4-mercapto-2-methylbutan-2-ylcarbamate (2.05 g, 8.1 mmol) in N,N-dimethylformamide (10 ml) was added cesium carbonate (2.27 g, 6.97 mmol) and 2-(2-(2-methoxyethoxy)ethoxy)ethyl 4-methylbenzenesulfonate (2.32 g, 7.29 mmol). The solution was heated to 60° C. for 2 hour, then 70° C. for 16 hour, cooled to room temperature, concentrated in vacuo, and the residue dissolved in 50 ml 5% NaHSO4, extracted with 3×50 ml ethyl acetate, dried on MgSO4, and concentrated in vacuo. The residue was purified by flash chromatography (10% to 60% ethyl acetate in hexanes) to give the title compound as a clear oil (1.24 g, 3.10 mmol, 60%). 1H NMR (400 MHz, CDCl3) δ 1.32 (s, 6H), 1.99 (m, 2H), 2.53 (m, 2H), 2.73 (m, 2H), 3.39 (s, 3H), 3.5-3.7 (m, 10H), 4.8 (s, 1H), 5.05 (s, 2H), 7.3-7.4 (m, 5H). LRMS (ESI/APCI) m/z 422 [M+Na]+.

Workup

temperaturecooled to room temperature
concentrationconcentrated in vacuo
dissolutionthe residue dissolved in 50 ml 5% NaHSO4
extractionextracted with 3×50 ml ethyl acetate
customdried on MgSO4
concentrationconcentrated in vacuo
customThe residue was purified by flash chromatography (10% to 60% ethyl acetate in hexanes)

Sources & evidence

ORD record: ord-78ae931894e543af944396da0354f892
Source dataset: uspto-grants-2016_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09248117B2

Reaction notes

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