Azidotrimethylsilane → ethyl 2-(9-azido-7-bromo-4-fluoro-2-methoxy-9H-xanthen-9-yl)acetate

HRID 455613Notes

Reaction equation

[Br:1][C:2]1[CH:15]=[C:14]2[C:5]([O:6][C:7]3[C:8]([F:25])=[CH:9][C:10]([O:23][CH3:24])=[CH:11][C:12]=3[C:13]2([CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])O)=[CH:4][CH:3]=1.[N:26]([Si](C)(C)C)=[N+:27]=[N-:28].C([O+]([B-](F)(F)F)CC)C>C1(C)C=CC=CC=1>[N:26]([C:13]1([CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])[C:12]2[CH:11]=[C:10]([O:23][CH3:24])[CH:9]=[C:8]([F:25])[C:7]=2[O:6][C:5]2[C:14]1=[CH:15][C:2]([Br:1])=[CH:3][CH:4]=2)=[N+:27]=[N-:28]

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of ethyl 2-(7-bromo-4-fluoro-9-hydroxy-2-methoxy-9H-xanthen-9-yl)acetate (1.0 g, 2.432 mmol) in toluene (25 ml) was added azidotrimethylsilane (0.560 g, 4.86 mmol). The solution was cooled to 0° C. and (diethyloxonio)trifluoroborate (0.308 ml, 2.432 mmol) was added drop wise. The mixture was stirred overnight at RT. The solution was quenched with MeOH (10 ml) and diluted with EtOAc. The organic phase was separated, washed with saturated aqueous sodium bicarbonate solution and brine, and then concentrated to afford crude ethyl 2-(9-azido-7-bromo-4-fluoro-2-methoxy-9H-xanthen-9-yl)acetate (1 g, 2.292 mmol, 94% yield).

Workup

customThe solution was quenched with MeOH (10 ml)
additiondiluted with EtOAc
customThe organic phase was separated
washwashed with saturated aqueous sodium bicarbonate solution and brine
concentrationconcentrated

Sources & evidence

ORD record: ord-bca0c6b09682426fb96c40b6b3296e02
Source dataset: uspto-grants-2013_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08497264B2

Reaction notes

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