1,4-Dioxane → (S)-2'-(neopentyloxy)-7'-(pyridin-2-yl)-5H-spiro[oxazole-4,9'-xanthen]-2-amine

HRID 335700Notes

Reaction equation

HRID 335700 reaction equation
Br[C:2]1[CH:15]=[CH:14][C:13]2[O:12][C:11]3[C:6](=[CH:7][C:8]([O:16][CH2:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[CH:9][CH:10]=3)[C@:5]3([CH2:25][O:24][C:23]([NH2:26])=[N:22]3)[C:4]=2[CH:3]=1.C([Sn](CCCC)(CCCC)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][N:33]=1)CCC.O1CCOCC1>CS(C)=O.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>[CH2:17]([O:16][C:8]1[CH:9]=[CH:10][C:11]2[O:12][C:13]3[C:4](=[CH:3][C:2]([C:32]4[CH:37]=[CH:36][CH:35]=[CH:34][N:33]=4)=[CH:15][CH:14]=3)[C@@:5]3([CH2:25][O:24][C:23]([NH2:26])=[N:22]3)[C:6]=2[CH:7]=1)[C:18]([CH3:19])([CH3:20])[CH3:21]

Participants

6

Reactant 3

HCID 312751,4-DioxaneHCID 6077842-(Tributylstannyl)pyridineHCID 58466128(R)-2'-bromo-7'-(neopentyloxy)-5H-spiro[oxazole-4,9'-xanthen]-2-amine

Product 1

HCID 58466301(S)-2'-(neopentyloxy)-7'-(pyridin-2-yl)-5H-spiro[oxazole-4,9'-xanthen]-2-amine

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
100 °C

Procedure

A vial was charged with (R)-2′-bromo-7′-(neopentyloxy)-5H-spiro[oxazole-4,9′-xanthen]-2-amine (0.050 g, 0.120 mmol), tetrakis(triphenylphosphine)palladium (0) (0.014 g, 0.012 mmol), 2-(tributylstannyl)pyridine (0.132 g, 0.359 mmol), and dioxane (0.6 mL). The reaction was stirred overnight at 100° C. The mixture was diluted with DMSO and filtered through a syringe filter, which was flushed with additional DMSO. The material was purified via Gilson HPLC (10-90% MeCN:H2O). The clean product fractions were partitioned between DCM and saturated sodium bicarbonate solution. The aqueous layer was extracted with DCM, and the combined organic layers were dried with sodium sulfate, filtered, and concentrated to afford (S)-2′-(neopentyloxy)-7′-(pyridin-2-yl)-5H-spiro[oxazole-4,9′-xanthen]-2-amine as a white solid. MS MH+ 416.4

Workup

  1. filtrationfiltered through a syringe
  2. filtrationfilter
  3. customwhich was flushed with additional DMSO
  4. customThe material was purified via Gilson HPLC (10-90% MeCN:H2O)
  5. customThe clean product fractions were partitioned between DCM and saturated sodium bicarbonate solution
  6. extractionThe aqueous layer was extracted with DCM
  7. dry with materialthe combined organic layers were dried with sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-83790d1528764e3f91dd56f9a76cafb9
Source dataset
uspto-grants-2014_11
Patent number
US08883782B2

Reaction notes

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