Ethanol → Tert-butyl 2-nitro-4-thien-3-ylphenylcarbamate

HRID 2093047Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[C:4]([N+:16]([O-:18])=[O:17])[CH:3]=1.C([O-])([O-])=O.[K+].[K+].C(O)C.[S:28]1[CH:32]=[CH:31][C:30](B(O)O)=[CH:29]1>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd].O>[N+:16]([C:4]1[CH:3]=[C:2]([C:30]2[CH:31]=[CH:32][S:28][CH:29]=2)[CH:7]=[CH:6][C:5]=1[NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])([O-:18])=[O:17]

Participants

Conditions

Temperature: 90 °C

Procedure

To a solution of tert-butyl 4-bromo-2-nitrophenylcarbamate obtained in step IV preparation 4 above (1.0 eq) in toluene, was added 10 mol % of tetrakis Pd, heated to 90° C. for 30 min, then aq K2CO3 and ethanol were added, followed by addition of 3-thienyl boronic acid portionwise and then reaction was refluxed overnight. Water was added to the reaction mixture and the organic layer was separated, dried over anhydrous Na2SO4 and concentrated under reduced pressure to afford crude product, which, on purification by column chromatography afforded the desired tert-butyl 2-nitro-4-thien-3-ylphenylcarbamate. (Yield=88%)

Workup

customreaction
temperaturewas refluxed overnight
customthe organic layer was separated
dry with materialdried over anhydrous Na2SO4
concentrationconcentrated under reduced pressure
customto afford crude product, which
customon purification by column chromatography

Sources & evidence

ORD record: ord-3360e11b41b74b16b8316c477c17ea66
Source dataset: uspto-grants-2013_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08440830B2

Reaction notes

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