Triphenylphosphine → HCID 86300601, compound

HRID 1024662Notes

Reaction equation

HRID 1024662 reaction equation
[CH3:1][O:2][C:3]1[CH:31]=[C:30]([O:32][CH3:33])[CH:29]=[CH:28][C:4]=1[CH2:5][NH:6][C:7]1[C:8]2[CH:15]=[CH:14][N:13]([C@H:16]3[C@@H:20]4[O:21][C:22]([CH3:25])([CH3:24])[O:23][C@@H:19]4[C@@H:18]([CH2:26]O)[O:17]3)[C:9]=2[N:10]=[CH:11][N:12]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.C1C=CC(OP(OC2C=CC=CC=2)([N:76]=[N+:77]=[N-:78])=O)=CC=1.C1C=CC(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)=CC=1>O1CCCC1>[N:76]([CH2:26][C@@H:18]1[C@H:19]2[O:23][C:22]([CH3:24])([CH3:25])[O:21][C@H:20]2[C@H:16]([N:13]2[C:9]3[N:10]=[CH:11][N:12]=[C:7]([NH:6][CH2:5][C:4]4[CH:28]=[CH:29][C:30]([O:32][CH3:33])=[CH:31][C:3]=4[O:2][CH3:1])[C:8]=3[CH:15]=[CH:14]2)[O:17]1)=[N+:77]=[N-:78]

Participants

7

Reactant 5

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 123414Diphenylphosphoryl azideHCID 199401P,P-Diphenylphosphinic azideHCID 67776590HCID 67776590, compound

Product 1

HCID 86300601HCID 86300601, compoundYield 83.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of ((3aR,4R,6R,6aR)-6-(4-((2,4-dimethoxybenzyl)amino)-7H-pyrrolo[2,3-d]pyrimidin-7-yl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-yl)methanol (2.83 g, 6.20 mmol) and triphenylphosphine (2.28 g, 8.68 mmol) in dry tetrahydrofuran (32 mL) was cooled at 0° C. in an ice/water bath. Diisopropyl azodicarboxylate (1.71 mL, 8.68 mmol) was added dropwise, followed by a solution of diphenylphosphonic azide (1.87 mL, 8.68 mmol) in tetrahydrofuran (5.3 mL, 66 mmol). Upon addition of the DPPA solution, a white milky precipitate formed. After about 30 minutes, the reaction mixture was allowed to warm to room temperature and stir overnight. After 24 h, HPLC indicated that all the starting material had been consumed. The reaction mixture was concentrated to about ½ the original volume and purified by flash chromatography (175 g silica gel, 10-55% EA/hept) to yield the title compound (2.49 g, 83%) as a slightly yellow stiff foam: MS (ESI+) for C23H27N7O5 m/z 482.2 (M+H)+; (ESI−) for C23H27N7O5 m/z 480.1 (M+H) m/z 526.1 (M+CO2H)−; HPLC purity 97% (ret. time, 3.64 min).

Workup

  1. customa white milky precipitate formed
  2. waitAfter 24 h
  3. customhad been consumed
  4. concentrationThe reaction mixture was concentrated
  5. custompurified by flash chromatography (175 g silica gel, 10-55% EA/hept)

Sources & evidence

ORD record
ord-cbb04ef894e04bd4a794300535a49dc8
Source dataset
uspto-grants-2014_05
Patent number
US08722877B2

Reaction notes

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