Tributyltin azide → HCID 71251271, compound

HRID 1055128Notes

Reaction equation

HRID 1055128 reaction equation
[F:1][C:2]1[C:3]([NH:18][CH:19]([C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:20][C:21]#[N:22])=[N:4][C:5]([C:8]2[C:16]3[C:11](=[N:12][CH:13]=[C:14]([F:17])[CH:15]=3)[NH:10][CH:9]=2)=[N:6][CH:7]=1.[N:27]([Sn](CCCC)(CCCC)CCCC)=[N+:28]=[N-:29]>O1CCOCC1>[CH3:24][C:23]([CH3:26])([CH3:25])[CH:19]([NH:18][C:3]1[C:2]([F:1])=[CH:7][N:6]=[C:5]([C:8]2[C:16]3[C:11](=[N:12][CH:13]=[C:14]([F:17])[CH:15]=3)[NH:10][CH:9]=2)[N:4]=1)[CH2:20][C:21]1[N:27]=[N:28][NH:29][N:22]=1

Participants

4

Reactant 2

HCID 4984872Tributyltin azideHCID 71251272HCID 71251272, compound2×

Product 1

HCID 71251271HCID 71251271, compound

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
130 °C

Procedure

To a solution of racemic 3-(5-fluoro-2-(5-fluoro-1H-pyrrolo[2,3-b]pyridin-3-yl)pyrimidin-4-ylamino)-4,4-dimethylpentanenitrile, 165a, (0.150 g, 0.420 mmol) in 10 mL of dioxane was added azido-tributylstannane (0.221 g, 0.668 mmol). The reaction vessel was sealed and warmed to 130° C. for 12 hours. Upon cooling, the reaction was concentrated to dryness and the resulting residue was purified by silica gel chromatography to afford 48 mg of desired product: 1H NMR (300.0 MHz, d6-DMSO) δ 12.23 (s, H), 8.49 (d, J=9.6 Hz, H), 8.26-8.05 (m, H), 4.03 (d, J=7.1 Hz, H), 3.48-3.35 (m, H), 3.17 (s, H), 2.50 (s, H), 1.99 (s, H), 1.13 (dt, J=25.1, 8.0 Hz, H), 1.01 (s, H), 0.96 (s, H) and 0.87 (d, J=6.6 Hz, H) ppm; LCMS Gradient 10-90%, 0.1% formic acid, 5 minutes, C18/ACN, Retention Time=1.94 minutes (M+H) 400.46.

Workup

  1. customThe reaction vessel was sealed
  2. temperatureUpon cooling
  3. concentrationthe reaction was concentrated to dryness
  4. customthe resulting residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-82b4f8f1a7dc451aa8fc4ea927ccd04c
Source dataset
uspto-grants-2016_07
Patent number
US09394302B2

Reaction notes

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