Methyl Acrylate → (S,E)-methyl 3-(2-amino-2'-bromo-5H-spiro[oxazole-4,9'-xanthene]-7'-yl)acrylate

HRID 1970379Notes

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.[C:22]([O:26][CH3:27])(=[O:25])[CH:23]=[CH2:24].P.C(N(CC)CC)C>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[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](/[CH:24]=[CH:23]/[C:22]([O:26][CH3:27])=[O:25])=[CH:9][CH:10]=1

Participants

Conditions

Temperature: 120 °C

Procedure

A mixture of (R)-2′-bromo-7′-iodo-5H-spiro[oxazole-4,9′-xanthen]-2-amine (3.00 g, 6.56 mmol), methyl acrylate (0.621 mL, 6.89 mmol), phosphine, tri-o-tolyl (0.400 g, 1.313 mmol), palladium(ii) acetate (0.295 g, 1.313 mmol), and triethylamine 99.5% (1.826 mL, 13.13 mmol) in DMF (12 mL) in a microwave vial was purged with argon for 5 min, capped, and heated to 120° C. for 40 min in a microwave. The reaction mixture was diluted with EtOAc (100 mL) and washed with water, dried over Na2SO4, and concentrated. The product was purified with ISCO using 0-70% EtOAc in hexanes to give (S,E)-methyl 3-(2-amino-2′-bromo-5H-spiro[oxazole-4,9′-xanthene]-7′-yl)acrylate. MS (ESI pos. ion) m/z: 416.9 (M+1).

Workup

customwas purged with argon for 5 min
customcapped
additionThe reaction mixture was diluted with EtOAc (100 mL)
washwashed with water
dry with materialdried over Na2SO4
concentrationconcentrated
customThe product was purified with ISCO

Sources & evidence

ORD record: ord-a26850b9e34f4267bd5ab196dcfda0a9
Source dataset: uspto-grants-2013_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08426447B2

Reaction notes

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