Triphenylphosphine → HCID 90411160, compound

HRID 1754608Notes

Reaction equation

HRID 1754608 reaction equation
[NH2:1][C:2]1[N:10]=[C:9]2[C:5]([NH:6][CH:7]=[N:8]2)=[C:4]([Cl:11])[N:3]=1.[CH2:12]([O:19][CH2:20][C@H:21]([C@H:24]([O:26][Si:27]([C:30]([CH3:33])([CH3:32])[CH3:31])([CH3:29])[CH3:28])[CH3:25])[CH2:22]O)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.C(OCC)(=O)C.CCCCCC>[CH2:12]([O:19][CH2:20][C@@H:21]([CH2:22][N:8]1[CH:7]=[N:6][C:5]2[C:9]1=[N:10][C:2]([NH2:1])=[N:3][C:4]=2[Cl:11])[C@H:24]([O:26][Si:27]([C:30]([CH3:31])([CH3:33])[CH3:32])([CH3:28])[CH3:29])[CH3:25])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 53603492-Amino-6-chloropurineHCID 5363146Diisopropyl azodicarboxylateHCID 11067317(2R,3R)-2-((benzyloxy)methyl)-3-(tert-butyldimethylsiloxy)butan-1-ol

Product 1

HCID 90411160HCID 90411160, compoundYield 75.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

To a cold (˜0° C., ice/water bath) mixture of 2-amino-6-chloropurine (2.2 g. 13.2 mmol), 4 (3.9 g, 12 mmol), triphenylphosphine (3.52 g, 13.4 mmol) in 50 ml of anhydrous THF was added with stirring 2.75 ml (13.9 mmol) of diisopropylazodicarboxylate. The reaction was stirred at room temperature for 5 hrs. The solvent was removed in vacuo and the residue chromatographed on silica eluting with a gradient of ethyl acetate (20-66%) in hexane. The product-containing fractions were pooled and concentrated to afford a semi-crystalline material, which was re-suspended in 20% ethyl acetate/hexane and filtered to remove insoluble hydrazine bis(isopropyl)carbamate. Concentration of the filtrate and drying in vacuo afforded 4.3 g (75%) of 24 as a white solid. 1H NMR, (DMSO-d6): δ 8.09 (s, 1H), 7.4-7.2 (m, 5H), 6.85 (s, 2H), 4.36 (s, 2H), 4.19 (m, 1H), 4.06 (m, 1H), 3.96 (m, 1H), 3.38 (m, 2H), 2.33 (m, 1H), 1.16 (d, J=6 Hz, 3H), 0.85 (s, 9H), 0.17 (s, 3H), 0.00 (s, 3H).

Workup

  1. additionwas added
  2. customThe solvent was removed in vacuo
  3. customthe residue chromatographed on silica eluting with a gradient of ethyl acetate (20-66%) in hexane
  4. concentrationconcentrated
  5. customto afford a semi-crystalline material, which
  6. filtrationfiltered
  7. customto remove insoluble hydrazine bis(isopropyl)carbamate
  8. customConcentration of the filtrate and drying in vacuo

Sources & evidence

ORD record
ord-3216d700bcb44209a7b6fffabcaf0243
Source dataset
uspto-grants-2015_10
Patent number
US09169256B2

Reaction notes

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