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2,6-Di-tert-butyl-4-methylphenol → Tert-butyl [3-(2-tert-butyl-4-cyano-5-methyl-6-phenyl-1,3-benzoxazol-7-yl)-2-cyclopentenyl]carbamate

HRID 17268
Notes
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Reaction equation

HRID 17268 reaction equation
Br[C:2]1[C:3]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[C:4]([CH3:17])[C:5]([C:15]#[N:16])=[C:6]2[C:10]=1[O:9][C:8]([C:11]([CH3:14])([CH3:13])[CH3:12])=[N:7]2.[C:24]([O:28][C:29]([NH:31][CH:32]1[CH2:36][CH2:35][C:34]([Sn](CCCC)(CCCC)CCCC)=[CH:33]1)=[O:30])([CH3:27])([CH3:26])[CH3:25].C(C1C(O)=C(C(C)(C)C)C=C(C)C=1)(C)(C)C>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCOCC1>[C:11]([C:8]1[O:9][C:10]2[C:2]([C:34]3[CH2:35][CH2:36][CH:32]([NH:31][C:29](=[O:30])[O:28][C:24]([CH3:26])([CH3:25])[CH3:27])[CH:33]=3)=[C:3]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C:4]([CH3:17])=[C:5]([C:15]#[N:16])[C:6]=2[N:7]=1)([CH3:12])([CH3:13])[CH3:14]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 314042,6-Di-tert-butyl-4-methylphenolHCID 15630117Tert-butyl (3-tri-n-butylstannylcyclopent-2-enyl)carbamateHCID 685849237-Bromo-2-tert-butyl-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrile

Product 1

HCID 86630798Tert-butyl [3-(2-tert-butyl-4-cyano-5-methyl-6-phenyl-1,3-benzoxazol-7-yl)-2-cyclopentenyl]carbamateYield 61%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalyst
HCID 312751,4-DioxaneSolvent

Procedure

A 1,4-dioxane (20 ml) solution of 7-bromo-2-tert-butyl-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrile (I-9) (414 mg, 1.12 mmol), 1-(N-tert-butoxycarbonylamino)-3-tri-n-butylstannyl-2-cyclopentene (530 mg, 1.12 mmol), bis(triphenylphosphine)palladium(II) chloride (39.3 mg, 56.1 μmol), 2,6-di-tert-butyl-p-cresol (28 mg, 127 μmol) was refluxed overnight. After cooling, the reaction liquid was concentrated under reduced pressure, the residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=10:1→8:1) to obtain tert-butyl [3-(2-tert-butyl-4-cyano-5-methyl-6-phenyl-1,3-benzoxazol-7-yl)-2-cyclopentenyl]carbamate (322 mg, 61%) as a yellow white solid. A part of it (270 mg) was stirred in hydrochloric acid/1,4-dioxane solution, followed by purifying by silica gel column chromatography to obtain 7-(3-amino-cyclopent-1-enyl)-2-tert-butyl-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrile (157 mg). This was dissolved in methanol (4 ml), aqueous formalin solution (324 μl, 46-38%, 4.23 mmol), sodium cyanoborohydride (80 mg, 1.27 mmol) and acetic acid (87 μl, 1.52 mmol) were successively added, followed by stirring at room temperature for 2.5 hours. The reaction liquid was concentrated under reduced pressure, aqueous 10% sodium carbonate solution was added to the residue, the organic matter was extracted with chloroform. The organic layer was washed with saturated brine, then dried over anhydrous magnesium sulfate, the solvent was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (chloroform:methanol=40:1) to obtain the entitled compound (84.8 mg, 50%) as a yellow solid.

Workup

  1. temperatureAfter cooling
  2. customthe reaction liquid
  3. concentrationwas concentrated under reduced pressure
  4. customthe residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=10:1→8:1)

Sources & evidence

ORD record
ord-11e8b026f97046df91548ee431019828
Source dataset
uspto-grants-2010_06
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07737166B2

Reaction notes

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