tert-Butanol → HCID 86681378, compound

HRID 1406681Notes

Reaction equation

HRID 1406681 reaction equation
[C:1]([C:3]1[CH:10]=[C:7]([CH:8]=[O:9])[C:6]([OH:11])=[CH:5][CH:4]=1)#[CH:2].[CH2:12]([N:19]=[N+:20]=[N-:21])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.CC(O)(C)C.O=C1O[C@H]([C@H](CO)O)C([O-])=C1O.[Na+]>O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Cu+2]>[CH2:12]([N:19]1[CH:2]=[C:1]([C:3]2[CH:4]=[CH:5][C:6]([OH:11])=[C:7]([CH:10]=2)[CH:8]=[O:9])[N:21]=[N:20]1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

7

Reactant 4

HCID 6386tert-ButanolHCID 12152Benzyl azideHCID 23667548Sodium AscorbateHCID 450835745-Ethynyl-2-hydroxybenzaldehyde

Product 1

HCID 86681378HCID 86681378, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 24463Copper sulfate pentahydrateCatalystHCID 962WaterSolvent2×

Procedure

5-ethynylsalicylaldehyde (2{26}, 50 mg, 0.34 mmol, 1.0 equiv.) and benzyl azide (91 mg, 86 μL, 0.68 mmol, 2.0 equiv.) were suspended in 1:1 t-BuOH:H2O (1.2 mL). Sodium L-ascorbate (24 mg in 100 μL H2O, 0.34 mmol, 1.0 equiv.) was added, followed by copper (II) sulfate pentahydrate (67 mg in 200 μL H2O, 0.10 mmol, 0.33 equiv.). The reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with H2O (10 mL), and the aqueous layer was extracted with DCM (3×10 mL). The combined organic layers were washed with brine (10 mL), dried over Mg504, filtered, and concentrated. The crude product was purified by silica gel column chromatography (25-50% EtOAc/hexanes) to yield 2{27} (47.5 mg, 0.17 mmol, 50.0%) as an off-white solid. 1H-NMR (500 MHz, CDCl3): δ 11.03 (s, 1H), 9.92 (s, 1H), 8.07 (d, 1H, J=2.5 Hz), 7.86 (dd, 1H, J=2.0, 8.0 Hz), 7.65 (s, 1H), 7.41-7.35 (m, 3H), 7.31 (dd, 2H, J=2.0, 7.5 Hz), 7.01 (d, 1H, J=8.5 Hz), 5.57 (s, 2H). 13C-NMR (125 MHz, CDCl3): δ 196.5, 161.3, 134.4, 134.2, 130.6, 129.1, 128.8, 128.1, 124.9, 122.9, 120.6, 118.9, 118.1, 54.3.

Workup

  1. extractionthe aqueous layer was extracted with DCM (3×10 mL)
  2. washThe combined organic layers were washed with brine (10 mL)
  3. customdried over Mg504
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe crude product was purified by silica gel column chromatography (25-50% EtOAc/hexanes)

Sources & evidence

ORD record
ord-3535624e74574f99b1bf74c87900e8ad
Source dataset
uspto-grants-2014_12
Patent number
US08916705B2

Reaction notes

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