2-Methyl-3-butyn-2-ol → HCID 59272308, compound

HRID 1970277Notes

Reaction equation

HRID 1970277 reaction equation
[Br:1][C:2]1[CH:15]=[CH:14][C:13]2[O:12][C:11]3[C:6](=[CH:7][C:8](I)=[CH:9][CH:10]=3)[C:5]3([CH2:20][O:19][C:18]([NH2:21])=[N:17]3)[C:4]=2[CH:3]=1.[CH3:22][C:23]([OH:27])([C:25]#[CH:26])[CH3:24]>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.[Cu]I.C1COCC1>[NH2:21][C:18]1[O:19][CH2:20][C:5]2([N:17]=1)[C:4]1[CH:3]=[C:2]([Br:1])[CH:15]=[CH:14][C:13]=1[O:12][C:11]1[C:6]2=[CH:7][C:8]([C:26]#[C:25][C:23]([CH3:24])([OH:27])[CH3:22])=[CH:9][CH:10]=1

Participants

6

Reactant 2

HCID 82582-Methyl-3-butyn-2-olHCID 58466329HCID 58466329, compound

Product 1

HCID 59272308HCID 59272308, compoundYield 64%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

To a 25 mL flask was added 2′-bromo-7′-iodo-5H-spiro[oxazole-4,9′-xanthen]-2-amine (536 mg, 1.173 mmol), bis(triphenylphosphine)palladium(II) chloride (82 mg, 0.117 mmol), copper(I) iodide (22.33 mg, 0.117 mmol). THF (10 ml), 2-methylbut-3-yn-2-ol (0.459 ml, 4.69 mmol) and DIPA (1.657 ml, 11.73 mmol) were added and the mixture was heated at 60° C. for 16 hrs. The mixture was filtered through Celite and concentrated. Separation on 12 g Redi-Sep column using 15-80% DCM/MeOH/NH4OH 90:10:1 in DCM gave 4-(2-amino-2′-bromo-5H-spiro[oxazole-4,9′-xanthene]-7′-yl)-2-methylbut-3-yn-2-ol (310 mg, 0.750 mmol, 64% yield) and ˜200 mg of symmetric product containing impurities, which was purified again using stacker of two 12 g Redi-Sep column, eluent 45-75% DCM/MeOH/NH4OH in DCM to afford 4,4′-(2-amino-5H-spiro[oxazole-4,9′-xanthene]-2′,7′-diyl)bis(2-methylbut-3-yn-2-ol).

Workup

  1. filtrationThe mixture was filtered through Celite
  2. concentrationconcentrated
  3. customSeparation on 12 g Redi-Sep column

Sources & evidence

ORD record
ord-a5e9c76ff01f4e8c82ea00a7a935611f
Source dataset
uspto-grants-2013_04
Patent number
US08426447B2

Reaction notes

Loading…