Triphenylphosphine → Purine

HRID 1241342Notes

Reaction equation

HRID 1241342 reaction equation
Cl[C:2]1[N:10]=[C:9](F)[N:8]=[C:7]2[C:3]=1[N:4]=[CH:5][NH:6]2.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[N:10]1[CH:2]=[C:3]2[C:7]([N:6]=[CH:5][NH:4]2)=[N:8][CH:9]=1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 178506011HCID 178506011, compound

Product 1

HCID 1044Purine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To the dried resin (0.29 mmol) was added a homogeneous suspension of 6-chloro-2-fluoro-9H-purine (0.50 g, 2.9 mmol) and triphenylphosphine (0.38 g, 1.44 mmol) in 1.75 mL of THF. The RV was cooled to 0° C. (Julabo chiller) and then added, under an atmosphere of N2, 2.0 mL (1.44 mmol) of a 0.72M solution of DEAD (diethyl azodicarboxylate) in THF. The resin mixture was warmed, while agitating, to ambient temperature over 1.5 h and then agitated for an additional 22 h, upon which the RV was drained and the resin washed successively with THF (5×5.0 mL), DMA (5×5.0 mL), CH2Cl2 (5×5.0 mL), Et2O (2×5.0 mL), CH2Cl2 (1×5.0 mL), Et2O (1×5.0 mL), and CH2Cl2 (2×5.0 mL). Excess solvent was removed via N2 flow overnight to provide the purine resin 1b. The following analytical data was obtained upon cleavage of 1b (3–5 mg) with 30% TFA/CH2Cl2 (˜5 min): 65% HPLC purity, ˜5:1 major/minor peaks (no apparent 3-hydroxyphenethyl alcohol HPLC peak).

Workup

  1. additionadded, under an atmosphere of N2
  2. temperatureThe resin mixture was warmed
  3. stirringagitated for an additional 22 h, upon which the RV
  4. washthe resin washed successively with THF (5×5.0 mL), DMA (5×5.0 mL), CH2Cl2 (5×5.0 mL), Et2O (2×5.0 mL), CH2Cl2 (1×5.0 mL), Et2O (1×5.0 mL), and CH2Cl2 (2×5.0 mL)
  5. customExcess solvent was removed via N2
  6. waitflow overnight

Sources & evidence

ORD record
ord-61f9933e35484acf99a9d4015ce9f56c
Source dataset
uspto-grants-2006_10
Patent number
US07115589B2

Reaction notes

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