Triphenylphosphine → 4-Chloro-7-cyclopropylmethyl-5-iodo-7H-pyrrolo[2,3-d]pyrimidine

HRID 244178Notes

Reaction equation

HRID 244178 reaction equation
[Cl:1][C:2]1[C:3]2[C:10]([I:11])=[CH:9][NH:8][C:4]=2[N:5]=[CH:6][N:7]=1.[CH:12]1([CH2:15]O)[CH2:14][CH2:13]1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[Cl:1][C:2]1[C:3]2[C:10]([I:11])=[CH:9][N:8]([CH2:15][CH:12]3[CH2:14][CH2:13]3)[C:4]=2[N:5]=[CH:6][N:7]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75644CyclopropanemethanolHCID 5363146Diisopropyl azodicarboxylateHCID 148092816-Chloro-7-iodo-7-deazapurine

Product 1

HCID 576808904-Chloro-7-cyclopropylmethyl-5-iodo-7H-pyrrolo[2,3-d]pyrimidine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of 4-chloro-5-iodo-7H-pyrrolo[2,3-d]pyrimidine (prepared according to: L. B. Townsend et al., J. Med. Chem. 1990, 33 (7), 1984-92) (419 mg, 1.50 mmol), cyclopropylmethanol (165 μL, 147 mg, 2.04 mmol), and PS—PPh3 (2.12 mmol/g; 1.41 g, 2.99 mmol) in dry THF (10 mL), cooled by ice/water, was added DIAD (440 μL, 452 mg, 2.23 mmol; 1.5 equiv.), then the cooling bath was removed and the mixture was vortexed overnight. The resin was filtered off and washed thoroughly with THF, and the filtrate and washings were combined and concentrated. Chromatography of the crude material thus obtained on silica gel (Jones Flashmaster, 2 columns, 10 g/70 mL cartridge each, eluting with CH2Cl2) gave the title compound as an off-white solid. 1H NMR (CDCl3, 400 MHz): δ=0.41-0.47 (m, 2H), 0.63-0.69 (m, 2H), 1.20-1.31 (m, 1H), 4.12 (d, J=7.2 Hz, 2H), 7.52 (s, 1H), 8.61 (s, 1H). MS (ES+): m/z 333.9/335.9 (100/38) [MH+]. HPLC: tR=3.7 min (OpenLynx, polar—5 min).

Workup

  1. customthe cooling bath was removed
  2. filtrationThe resin was filtered off
  3. washwashed thoroughly with THF
  4. concentrationconcentrated
  5. customChromatography of the crude material thus obtained on silica gel (Jones Flashmaster, 2 columns, 10 g/70 mL cartridge each,
  6. washeluting with CH2Cl2)

Sources & evidence

ORD record
ord-f505383fae3e4ac4a15eba6908699c92
Source dataset
uspto-grants-2014_02
Patent number
US08653268B2

Reaction notes

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