Phosphonium, (bromomethyl)triphenyl-, bromide (1:1) → HCID 21021579, compound

HRID 1793798Notes

Reaction equation

HRID 1793798 reaction equation
CC(C)([O-])C.[K+].[Br-].[Br:8][CH2:9][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH:29]1([NH:34][C:35]2[N:43]=[CH:42][N:41]=[C:40]3[C:36]=2[N:37]=[CH:38][N:39]3[C@H:44]2[CH:51]3[C@H:47]([O:48][C:49]([CH3:53])([CH3:52])[O:50]3)[C@@H:46]([CH2:54][CH:55]=O)[O:45]2)[CH2:33][CH2:32][CH2:31][CH2:30]1>O1CCCC1>[Br:8]/[CH:9]=[CH:55]/[CH2:54][C@@H:46]1[C@@H:47]2[CH:51]([O:50][C:49]([CH3:53])([CH3:52])[O:48]2)[C@H:44]([N:39]2[CH:38]=[N:37][C:36]3[C:40]2=[N:41][CH:42]=[N:43][C:35]=3[NH:34][CH:29]2[CH2:30][CH2:31][CH2:32][CH2:33]2)[O:45]1

Participants

5

Reactant 3

HCID 2733422Phosphonium, (bromomethyl)triphenyl-, bromide (1:1)HCID 23665647Potassium tert-butoxideHCID 86591275HCID 86591275, compound

Product 1

HCID 21021579HCID 21021579, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a stirred solution of potassium-tert-butoxide (0.78 g, 6.93 mmol) in tetrahydrofuran (45 mL) was added (bromomethyl)triphenylphosphonium bromide (1.51 g, 3.27 mmol) in small portions at −78° C. The resulting mixture was stirred at −78° C. for 2 hours. 2-{(1R,2R,4R)-4-[6-(cyclopentylamino)purin-9-yl]-7,7-dimethyl-3,6,8-trioxabicyclo[3.3.0]oct-2-yl}ethan-1-one, a compound of Formula (11) (0.89 g, 2.31 mmol) dissolved in THF (15 mL) was added slowly and the mixture stirred under an atmosphere of N2 at −78° C. for 3 hours, brought to room temperature slowly and stirred for 4 days. The reaction mixture was quenched with saturated NH4Cl aqueous solution (15 mL) and diluted with H2O (60 mL), and then extracted with EtOAc (3×50 mL). The combined organic layers were washed with H2O (2×50 mL), dried over Na2SO4, and evaporated under reduced pressure, to provide {9-[4-((2E)-3-bromoprop-2-enyl)(2R,4R,5R)-7,7-dimethyl-3,6,8-trioxabicyclo[3.3.0]oct-2-yl]purin-6-yl}cyclopentylamine, a compound of formula (12), which was isolated by column chromatography.

Workup

  1. additionwas added slowly
  2. stirringthe mixture stirred under an atmosphere of N2 at −78° C. for 3 hours
  3. custombrought to room temperature
  4. stirringstirred for 4 days
  5. customThe reaction mixture was quenched with saturated NH4Cl aqueous solution (15 mL)
  6. additiondiluted with H2O (60 mL)
  7. extractionextracted with EtOAc (3×50 mL)
  8. washThe combined organic layers were washed with H2O (2×50 mL)
  9. dry with materialdried over Na2SO4
  10. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-21f045d12e6c4d66a0e70befc3dff4ff
Source dataset
uspto-grants-2006_04
Patent number
US07022681B2

Reaction notes

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