Cesium carbonate → (S)-3-(4-(1H-benzo[d][1,2,3]triazol-1-yl)phenyl)-5,5-dimethyl-4-phenyloxazolidin-2-one

HRID 525382Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C@@H:12]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[C:11]([CH3:20])([CH3:19])[O:10][C:9]2=[O:21])=[CH:4][CH:3]=1.[NH:22]1[C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][C:25]=2[N:24]=[N:23]1.CC1C=NC2C(C=1C)=CC=C1C=2N=CC(C)=C1C.C(=O)([O-])[O-].[Cs+].[Cs+]>CS(C)=O.[Cu]I>[N:22]1([C:2]2[CH:7]=[CH:6][C:5]([N:8]3[C@@H:12]([C:13]4[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=4)[C:11]([CH3:20])([CH3:19])[O:10][C:9]3=[O:21])=[CH:4][CH:3]=2)[C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][C:25]=2[N:24]=[N:23]1

Participants

Conditions

Temperature: 140 °C

Procedure

A glass microwave reaction vessel was charged with (S)-3-(4-bromophenyl)-5,5-dimethyl-4-phenyloxazolidin-2-one (100 mg, 0.289 mmol), benzotriazole (25.3 μL, 0.289 mmol, commercially available from Sigma-Aldrich, Milwaukee, Wis.), copper (I) iodide (5.50 mg, 0.029 mmol, commercially available from Sigma-Aldrich, Milwaukee, Wis.), 3,4,7,8-tetramethyl-1,10-phenanthroline (27.3 mg, 0.116 mmol, commercially available from Sigma-Aldrich, Milwaukee, Wis.) and cesium carbonate (188 mg, 0.578 mmol) in DMSO (578 μL). The reaction mixture was stirred and heated in a heating block at 140° C. for 4 hours. LC-MS indicated complete conversion to the desired product. After cooling to room temperature, the reaction mixture was passed through a syringe filter. The material thus obtained was purified by reverse-phase preparative HPLC using 0.1% TFA in ACN/H2O, gradient 20% to 90% over 20 minutes. The pure fractions were combined and diluted with 30% ammonium hydroxide, and the aqueous layer was extracted with DCM (3×20 mL) to provide (S)-3-(4-(1H-benzo[d][1,2,3]triazol-1-yl)phenyl)-5,5-dimethyl-4-phenyloxazolidin-2-one (10 mg, 0.026 mmol, 9.01% yield) as a white solid. 1H NMR (500 MHz, DMSO-d6) δ 8.15 (d, J=8.33 Hz, 1H), 7.85 (d, J=8.33 Hz, 1H), 7.77-7.84 (m, 4H), 7.62 (dd, J=7.16, 7.91 Hz, 1H), 7.50 (d, J=7.48 Hz, 1H), 7.38-7.44 (m, J=7.60 Hz, 2H), 7.29-7.37 (m, 3H), 5.57 (s, 1H), 1.68 (s, 3H), 0.94 (s, 3H). m/z (ESI) 385.2 (M+H)+.

Workup

customA glass microwave reaction vessel

Sources & evidence

ORD record: ord-215ed9a2d5df4de4855837631b352b01
Source dataset: uspto-grants-2016_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09340549B2

Reaction notes

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